Timing the delivery of D-backs right-hander Max Scherzer, Matthews broke for home on a 1-2 pitch that sailed high to Erick Aybar. Catcher Miguel Montero strained to get a tag down, but Matthews maneuvered away from him with a classic hook slide, giving the Angels a 4-2 lead in an eventual 12-8 win.
It was the second career steal of home by Matthews, who prides himself on being an old-school player in his father's image, and the first by an Angels player since Orlando Cabrera turned the trick against the Dodgers on July 2, 2006.
"The first one [in 1999] was on the back end of a double steal," Matthews said. "This was my first straight steal.
"They're definitely not expecting it with two strikes. With a right-handed hitter, it's dangerous. With a left-handed hitter [Aybar], he can see you coming. We pulled it off."
Matthews, who moved within two hits of 1,000 with his double, was surprised to get the "go" sign from manager Mike Scioscia via third-base coach Dino Ebel.
"Dino told me they gave the green light from the dugout," Matthews said. "He said, `Take a shot if you want.' With two strikes, I thought I could get a really good jump and be on top of everybody before he had a chance to swing the bat on me. I tried to time it right and got a pretty big lead."
Watching from the dugout, Scioscia was confident Matthews could make it happen.
"At the very end [of his delivery], it looked like [Scherzer] jumped a little bit," Scioscia said. "Gary had a great read at third base. He had the timing perfectly, and if he did, we felt comfortable he'd beat it."
It was the third time in franchise history Arizona had allowed a steal of home and the first since Sept. 30, 2005, at San Francisco by the Giants' Edgardo Alfonzo.
Matthews, playing in center field with Hunter getting a day off to rest his weary legs, seemed to unravel the D-backs with his daring move. They committed three errors in the fifth inning, all on routine plays, committed by first baseman Mark Reynolds, right fielder Justin Upton and second baseman Felipe Lopez.
The Angels had been thrown out stealing twice in the first three innings, but nothing deters them from their familiar aggression on the bases.
They rank second in the American League in steals behind the Rays and have gone first to third on singles more often than any team in the Majors.