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That was not Jack Donaghy of “30 Rock” talking to the Democratic candidate for New York City mayor, Bill de Blasio, on MSNBC, nor was it the slimy businessman in “Blue Jasmine.” It wasn’t even the daffy salesman from those Capital One credit card ads. (“What’s in your wallet?”)

Alec Baldwin stripped off all his comic personalities Friday for a new weekly talk show on MSNBC, “Up Late With Alec Baldwin,” which he says will be “more conversation than interview.” And he started off his gig by chatting with de Blasio, whom he supported in the primary. Baldwin looked friendly and informed, inquisitive and, for a while at least, self-effacing — he even kept a lid on his famously volcanic temper. And the result was: Charlie Rose.

Over coffee in a saloonlike booth with wood paneling and green leather banquettes, the two men talked earnestly about de Blasio’s plan for, as he put it, “a more activist and aggressive government.” Baldwin ticked off de Blasio’s proposals to raise taxes on the rich, to build more affordable housing and to expand prekindergarten programs.

“What I don’t see here,” Baldwin said, “is job creation.” He didn’t ask de Blasio how he planned to deal with union contracts, which may be the most difficult and pressing mayoral task ahead, but the two men did discuss Wall Street, marijuana (de Blasio is not in favor of full legalization), the police, the Bloomberg era, and even their childhoods and marriages.

It was a long and not always sparkling exchange, but it was in some ways quite illuminating about the candidate, and also MSNBC.

Viewers got a close-up look at de Blasio, who has largely kept out of sight since winning the primary and instead courted business tycoons and wealthy donors behind closed doors on Park Avenue, in Gramercy Park and at breakfast at the Yale Club. And on television, at least, de Blasio, a grandson of Italian immigrants who was raised by a single mother and was once a supporter of the Sandinistas, sounded smoothly self-assured, and even a little patrician.

When Baldwin made a teasing suggestion about how to persuade New York Gov. Andrew M. Cuomo to condone his tax plan, de Blasio archly replied, “You are mischievous, sir.”

Baldwin did look a little impish – a few spikes of hair above his forehead were twisted with gel into tiny devils’ horns – but his tone was respectful. And when an actor as passionate and colorful as Baldwin seems like a school librarian next to his cable colleagues, it says something about the excitable nature of most so-called news shows.

MSNBC hired a movie star, yet it’s the regular anchors like Martin Bashir and Chris Hayes who declaim like hyped-up Hollywood divas. Guests on these kinds of shows are not asked questions, they are held hostage to split-screen harangues. (Lawrence O’Donnell’s infamous “What is wrong with you?” screed at Anthony D. Weiner, the sext-obsessed former Democratic congressman, was a classic of the genre.)

Baldwin, who is a longtime liberal activist and for a while had his own podcast on WNYC radio, is an engaging host who asks serious questions about economic policy and politics, but he became most animated talking about romance.

De Blasio is married to Chirlane McCray, an African-American who was a lesbian when they met, and he has made his marriage and mixed-race family a highlight of his campaign. (Baldwin described the candidate’s gauzy Reagan-esque ads showing the candidate at breakfast with his wife and son as “It’s morning in Park Slope.”)

De Blasio said that he knew that he and McCray were soul mates when they attended the New York African Film Festival at Lincoln Center in 1993, and enjoyed it so much they saw 21 movies on the program.

Baldwin volunteered the story of how he fell for his current wife, Hilaria, who was a 20-something yoga instructor when they met in 2011.

“I remember during my lifetime I would meet women, and it was almost like God would say to me, ‘Now, this woman here is not the one you are going to end up with, but she is going to be a lot like this woman; look at this woman, study this woman,’ ” Baldwin said, speeding up so de Blasio couldn’t interrupt. “And when my wife showed up, he was like, ‘You recognize her now?’ ”

Audiences rarely fall in love with talk-show hosts at first sight, but on opening night, Baldwin more than delivered on his promise that his show would be “more personal than promotional.”