"Yeah, we watched it, because we didn't even know this whole thing about woman No. 4 was going to even come out, so that was a surprise," Cain said.
Bialek is the fourth woman to allege sexually inappropriate behavior by Cain, but the first to speak publicly. She was a former employee of a foundation tied to the National Restaurant Association when Cain was president of the trade group.
"At least this wasn't the one of many who have the first name ‘anonymous,’ so now this one actually had a name and a face, so we watched to see what it was, who it was," Cain added.
Cain has been critical of the anonymous nature of the allegations leveled against him since reports first surfaced last week of sexual harassment charges against him from two unnamed women while he was the head of the restaurant association in the 1990s.
The GOP contender denied the accusations and said "there is not an ounce of truth" to any of them.
Cain's appearance Monday night started off on a lighter tone, with Kimmel asking, "How was your day?"
He responded, "Well, all things considered, I'm still alive. It got off to somewhat of a rough start. We had [a] little surprise ... show up on TV."
The former Godfather's Pizza CEO vowed to publicly address the most recent allegations raised against him.
He said he will be holding a press conference Tuesday to address the latest charges.
"I will talk about any and all future firestorms, because here's one thing people don't know about Herman Cain: I'm in it to win it."