"For the record, have you ever used steroids, human growth hormone or any other performance-enhancing substance?" Couric asked.
"No," Rodriguez replied.
Asked if he had ever been tempted to use any of those things, Rodriguez told Couric, "No."
"You never felt like, 'This guy's doing it, maybe I should look into this, too? He's getting better numbers, playing better ball,'" Couric asked.
"I've never felt overmatched on the baseball field. I've always been a very strong, dominant position. And I felt that if I did my work as I've done since I was, you know, a rookie back in Seattle, I didn't have a problem competing at any level. So, no," he replied.
But the Mitchell Report named names, including at least 16 current and former Yankees, like superstars Andy Pettitte and Roger Clemens.
What's Rodriguez's reaction to this investigation?
"Katie, you're putting me in a tough spot. I mean, these are guys that I play with. They're my teammates. If anything comes of this, I will be extremely disappointed. And it will be a huge black eye on the game of baseball," he told Couric.
"It sounds like this is rampant. According to the Mitchell Report, every single club has a player using banned substances. Did you ever witness or hear about or even suspect this was going on?" Couric asked.
"You hear a lot of things. I mean, I came in 1993. And you heard whispers from the '80s and '90s. But I never saw anything. I never had raw evidence. And, quite frankly, I was probably a little bit too naïve when I first came up to understand the magnitude of all this," Rodriguez replied.
But there’s no escaping the magnitude of the scandal now. The Mitchell Report comes on the heels of Barry Bonds' recent indictment in San Francisco for perjury and obstruction of justice in a federal steroids investigation.
"Given this controversy, Alex, who do you think has the real homerun record? Barry Bonds at 762 or Hank Aaron 755?" Couric asked.
"Well, I think Barry Bonds. He has 762," Rodriguez said.
"But, he has an asterisk next to his name?" Couric remarked.
"Does he?" Rodriguez said. "Not yet."
"In the minds of many, he does," Couric said.
"The federal government is going to make its decision on that. Barry's been a phenomenal player. And I've really enjoyed watching him play. But, he's innocent 'til proven guilty," Rodriguez replied.
On the same day the Mitchell Report was front page news, A-Rod was making headlines as well. The Yankees announced he had been re-signed, breaking his own record-setting deal. He already had the highest paying contract in any team sport.
Asked why he thinks he gets so much grief over his salary, Rodriguez told Couric, "'Cause I make a lot of money."
"Your new contract is worth $300 million-plus. Are you worth it? Is any player worth that kind of salary?" Couric asked.
"I'm not sure," Rodriguez said. "I mean, that's not my job to evaluate or appraise players. I love to play baseball."
Katie Couric spoke with him just after the Mitchell Report was released.