The American's fate, and that of South Korean Park Tae-hwan in the 200m freestyle, demonstrated the unpredictablity of a world championships that has produced 11 world records through the first two days.
Five of those came on Monday, as swimmers continued to exploit the availability of high-tech supersuits that are to be banned from 2010.
But Peirsol, who races in a part-polyurethane Arena suit, said it was his own mistake that cost him a shot at a fourth straight 100m backstroke world title.
"We're all wearing suits," said Peirsol, who had won the title at the 2003, 2005 and 2007 world championships, as well as claiming Olympic gold in 2004 and 2008. He lowered the 100m backstroke world record earlier this month at the US trials.
"That was a huge miscalculation," Peirsol said of his fourth-placed finish in his semi-final. "I thought I was in a much better place in that race than I was.
"Usually I'm not that bad (at judging his pace), I wasn't completely reserving there, I just thought I was in a place that I wasn't in. That was my own fault."
Olympic superstar Michael Phelps made it safely into the final of the 200m freestyle, but the world record-holder settled for winning his heat in the third-fastest time of the night.
Germany's Paul Biedermann, who eclipsed Ian Thorpe's iconic 400m freestyle world record on Sunday, was the top qualifier from the 200m free semis with a time of 1:43.65.
Phelps, who holds the world record of 1:42.96, won his heat in 1:45.23, and said the key to competing in Rome was shutting out the record chatter.
"You really have to race your race," he said. "People are swimming really fast right now.
"I think the basic thing is you have to swim your own race and you can't worry about what anybody else is doing."
Biedermann's time, however, clearly got Phelps's attention.
"He did 1:43?" Phelps said. "He has dropped a lot of time. Usually you don't see six seconds drop in a 400 in a year. I think he was in the final last year in the 200 free and he has dropped three seconds over the last year in that. So he's having a good meet, he's having a good year."
Biedermann has said he believes his polyurethane Jaked suit gives him extra seconds, but Phelps again refused to be drawn into the swimsuit controversy.
"I'm not here to talk about the suit. I'm here to swim in the World Championships," he said.
Instead Phelps, winner of an unprecented eight gold medals at the Beijing Olympics, said he had to concentrate on getting ready for his first day of double-duty on Tuesday, when he'll race the heats and semis of the 200m butterfly as well as the 200m free final.
The world record roll-call included two women who set world marks for the second time in as many days - Swedish teenager Sarah Sjostrom and American Ariana Kukors.
Sjostrom clocked 56.06 to win the 100m butterfly title ahead of Australian Jessicah Schipper and China's Jiao Liuyang.
Kukors posted a stunning 2:06.15 to win the women's 200m individual medley.
Kukors had lowered the world mark to 2:07.03 in the semi-finals - already an impressive improvement on the previous mark of 2:08.45 held by Australian triple Olympic gold medallist Stephanie Rice.
Rice admitted she had no answer as she took silver ahead of Hungarian Katinka Hosszu.
Australian Brenton Rickard also had a world title to go with his world record in the men's 100m breaststroke. He won in 58.58sec to eclipse the mark that Japan's Kosuke Kitajima established en route to Olympic gold in Beijing. France's Hugues Duboscq was second and South Africa's Cameron Van Der Burgh third.
Serbian Milorad Cavic claimed a rare gold medal unaccompanied by a world record, winning the 50m freestyle in 22.67sec ahead of Australian Matthew Targett and Spain's Rafael Munoz.
Two other world marks fell in semi-finals, Olympic silver medallist Rebecca Soni breaking the 100m breaststroke mark with a time of 1:04.84, and Russian Anastasia Zueva leading the way into Tuesday's 100m backstroke final with a world mark of 58.48.
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