Grimsley, a former reliever, is part of an active investigation on performance-enhancing drugs by the Internal Revenue Service, and he named several players and former teammates in a wide-ranging interview with IRS field agents.
Those names were redacted in the public version of the affadavit, but Segui claimed to be the player that told Grimsley where he could get human growth hormone.
Segui, who spent 15 years in the Majors and retired in 2004, said on the ESPN program that he continues to use HGH legally. Segui added that he used the drug with a doctor's prescription because of a growth hormone deficiency. He said he first started using the hormone after the deficiency was found when he went for blood work before surgery during his playing career.
The 39-year-old first baseman said Grimsley came to him this past offseason, seeking advice about HGH and how it might help him recover from major arm surgery. Grimsley was waived by the Diamondbacks this month after acknowledging HGH use and accusing other players of its use in a statement to federal agents.
The two played together in Baltimore in 2004, and Segui is currently out of baseball. Earlier this month, Grimsley was released by Arizona and suspended 50 games by Major League Baseball.
"I didn't hear all of it. Just a sort bleep on the news this morning, so I don't have all the facts on that yet," said Orioles skipper Sam Perlozzo said. "It's not a reflection on the organization. I think that's where people get caught up, in the fact that they think the organization was a part of this deal. All these things that you see, for me, are strictly personal decisions that people make."
Next week, Perlozzo and other members of Baltimore's front office are scheduled to speak with the league's committee investigating performance-enhancing drugs in the game. Former Senate majority leader George Mitchell is chairing that committee and reportedly wants to speak with front-office emissaries from all 30 teams.
The Associated Press contributed to this report. This story was not subject to the approval of Major League Baseball or its clubs.