Anyika Onuora, Montell Douglas, Hayley Jones and Ashlee Nelson finished second in their semi-final behind Germany in a time of 43:51 seconds. However, they were subsequently disqualified after Jones stepped out of her lane taking one of the notoriously tight bends on the Helsinki track.
Team officials appealed, but the video evidence was clear – and the result drops Britain outside the world's top 16 and therefore out of the 2012 Games.
"This was an accident waiting to happen, we have been under performing in this area for probably 10 years,” said UKA head coach van Commenee.
"I'm not really surprised: it's the reason why I stopped funding the programme two years ago because I didn't think they could be dangerous in London.
"We are not finalists, we are ranked somewhere between 15th and 20th in the world and unfortunately we're [now] 17th.
"I don't want to play down the fact it's a home Games and you obviously want a team there, it's not good at all.
"I am fully aware that not going to the Games was not a result of failing here, it is a result of 10 or 20 years of not producing.
"They were emotional, all four. I must say that not only these four, every athlete here who has a last hope to get the Olympic qualifier in and fails to do so is very depressed."
The team did make the final at the Beijing Olympics, although they were subsequently disqualified.
However Van Commenee defended his stance on team funding.
"I can spend the pound only once, so I have to make choices,” he said. “The programme is always focused on medallists first, then finalists, then who could be a finalist, and the rest are not looked after, basically."
The error in Helsinki saw Russia bumped up to second place, with Netherlands taking the third and final automatic place in the final. Sweden were also excluded after finishing last in the same race.
Defending champions Ukraine powered into the final, winning the first semi in a time of 42.70. France were second and Poland third, mirroring the result of the 2010 final. Slovenia’s team - which included Jamaican-born three-time world 100m champion Merlene Ottey, racing at the age of 52 in the hope of competing in an eighth Olympic Games – came seventh.
Britain’s men qualified for the final of their 4x100 relay with no problems, setting up a tantalising final duel against France.
The quartet of Christian Malcolm, Dwain Chambers, James Ellington and Mark Lewis-Francis stormed to victory in their heat during Saturday’s morning session in a time of 38.98.
A France team including reigning European 100m champion Christophe Lemaitre and silver-medallist Jimmy Vicaut were pushed hard by Germany, but Vicaut out-sprinted Martin Keller at the last to take the heat in a time of 39.01.
Russia’s Sergey Shubenkov followed up on the form which recently won him the European under-23 title in the men’s 110m hurdles by coming through the heats with a fastest time of 13.28. France’s Garfield Darien, runner-up in 2010, was second quickest while Hungary’s Daniel Kiss, bronze medallist in Barcelona, also progressed.
With reigning champion Andy Turner not present as he competes for his place in Team GB’s Olympic squad, British interest in the event hinges on William Sharman and Gianni Frankis, the latter coming through the heats as a fastest loser. Fellow Brit Richard Alleyne failed to make it out of the heats.
Nuria Fernandez qualified for the final of the women’s 1500m, with the Spanish defending champion taking the final of the eight automatic places after her run in the second semi-final, which was won by favourite Yekaterina Gorbunova of Russia.
Britain’s Charlene Thomas led the first semi-final for a time before being drawn back into the pack at the bell, and she was eventually disqualified for briefly stepping off the track.
Britain’s Jade Nicholls fell well short of reaching the final of the women’s discus, finishing outside of the top 20 in qualifying. Defending champion Sandra Perkovic of Croatia safely reached the final, although her distance was almost 2.5 metres shorter than the best of 64.49 from Germany’s Nadine Mueller.
There will be three new medallists in the men’s 1500m after 2010’s silver and bronze winners Carsten Schlangen and Manuel Olmedo failed to make it through their semi-finals, with current champion Arturo Casado already missing from Helsinki through injury. Britain’s Tom Lancashire also fell out after only finishing 10th in his race.
France’s Renaud Lavillenie looked on course to defend his European men's pole vault title as he was one of three competitors to record a best height of 5.55 in qualifying. Britain’s Max Eaves narrowly failed to reach the final on count-back after making the vault of 5.30 that saw two of his rivals progress.
Ida Antoinette Nana Djimou of France is well poised to win the heptathlon after her personal best throw of 55.82 in the javelin gave her a 162-point lead going into Saturday evening’s final event, the 800m.
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