Despite his planning, Kaine ended up second in line -- perhaps also appropriate for the potential vice president.
Kaine told CNN's "New Day" that he "got to my polling place about a quarter until 6," and that "there was already a line" when he arrived.
The Virginia senator was beaten to the polls by 99-year old Minerva Turpin.
"Well, Ms. Turpin gave me reason to believe that I might win her vote. I voted at a senior center that's two blocks from my house. She is the president of the residents' association. So she welcomed me -- she was the first voter, I was the second voter. She pinned my 'you voted' stick on after I completed my ballot," he said.
Kaine added: "We think that there's going to be huge turnout. And that is good news for democracy when people participate."
"Look, you know, we're a closely divided nation. We feel really good about the Hillary coalition, the coalition of voters of all income levels, of all races around this country that are turning out in early vote in ways that make us feel good about the likely outcome," he said.
Kaine also talked about playing the harmonica with Jon Bon Jovi at an Election Day eve rally.
"We had a great time playing 'You Give Love a Bad Name,' " he said. "I played a lot of harmonica on the trail. I would say that, and being able to speak Spanish, are the two fun things I've been able to do during my 105-day adventure. Being with Jon Bon Jovi on stage, hard to beat that."