Baseball writers elected four players for the first time since 1955, with Martinez, Johnson and Smoltz earning induction on the first try Tuesday. Biggio made it on the third attempt after falling two votes shy last year.
The quartet will be inducted in Cooperstown on July 26.
The Baseball Writers' Association of America had not given four players the necessary 75 percent in a single year since selecting Joe DiMaggio, Gabby Hartnett, Ted Lyons and Dazzy Vance 60 years earlier.
Johnson, a five-time Cy Young Award winner, was selected on 97.3 percent of the 549 ballots cast this year.
Martinez, who won three Cy Young Awards, was on 91.1 percent of the ballots while Smoltz and Biggio received 82.9 and 82.7 percent of the votes, respectively.
The Associated Press contributed to this report.