Billboard was the first to report that "One" would be the sixth radio single from "Dream" Sept. 14.
"I'm so pleased to select 'The One That Got Away' as my sixth single because this song shows a very different side of me that I haven't shown with my past singles on this record," Perry said in a statement from the label. "I think that everyone can relate to this song. I wrote (it) about when you promise someone forever, but you end up not being able to follow through.
"It's a bittersweet story. Hopefully, the listener learns from hearing it and never has to say they had 'The One' get away."
The first five singles from "Dream" - "California Gurls," featuring Snoop Dogg; the title cut; "Firework"; "E.T.," featuring Kanye West; and, "Last Friday Night (T.G.I.F.)" - all reached the Hot 100's summit, making Perry the first woman to notch five No. 1s on the chart from one album.
Michael Jackson is the only other artist to have accomplished the feat, having scored five leaders from "Bad" in 1987-88.
Katy Perry Makes Hot 100 History: Ties Michael Jackson's Record
"If it goes to No. 1, that would be great," EMI Music/Capitol Records EVP/marketing and promotion Greg Thompson told Billboard two weeks ago. "If not, we still have a Katy song on the radio in fourth quarter," likely fueling further sales for "Dream" in the bustling shopping season.
Ahead of its official push, "One" made early strides at radio in the past seven days (Sept. 21-27). The song improved from eight to 106 plays on the more than 1,200 stations monitored by BDS for the Hot 100.
KHTT (106.9 K-HITS)/Tulsa, Okla., led with 30 plays for "One" (up 25) in that span, followed by KQCH (Channel 94.1)/Omaha, Neb. (25, up 22), and WNKS (Kiss 95.1)/Charlotte, N.C. (21 first-week spins).
KHTT first sampled the song Aug. 23, 2010, the day before "Dream" was released to retail. The set, which topped the Billboard Hot 100 upon its debut, has sold 1.8 million copies in the U.S., according to Nielsen SoundScan.
As an album track, "One" has sold 77,000 downloads.
A video for "One" will be shot "in the coming days," according to Capitol. Also potentially aiding the song's cause are more tour dates for Perry. Her California Dreams World Tour that began earlier this year with stops in Europe, Australia, New Zealand and Japan continues with five dates next month, including a show at New York's Madison Square Garden Nov. 16, before the tour wraps, fittingly in the Golden State, at Los Angeles' Staples Center Nov. 22.