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Williams, who had last won a Grand Slam title here two years ago, first overpowered and then outlasted the 23-year-old Radwanska, 6-3, 5-7, 6-2. Radwanska was playing in her first Grand Slam final.
Shortly after Williams, 30, dominated the 2010 Wimbledon championships, she had a foot injury that required surgery and then a pulmonary embolism that combined to keep her away from tennis for almost a year.
She made her return to majors tennis here a year ago but was upset in the fourth round. Williams suffered an unexpectedly decisive loss in the finals of the 2011 U.S. Open to Samantha Stosur, then lost in the fourth round of the 2012 Australian Open and in the first round of the French Open last May.
But Williams, seeded sixth, overpowered the field here. In the second game of the second set against the Radwanska, Williams set a new Wimbledon women's record with her 90th ace and that stellar serving kept all her opponents off balance.
Williams got better as the tournament progressed. She survived 25th-seeded Jie Zheng of China by winning 6-7 (5), 6-2, 9-7 in the third round and she needed all three sets to win her fourth-round match against Yaroslava Shvedova, 6-2, 2-6, 7-5.
"I can't even describe it. I almost didn't make it," Williams said. "A few years ago, you know, I was in the hospital, and now I'm here again. It's so worth it, and I'm so happy."
It seemed as if Williams was on the way to a blowout win when she broke Radwanska at love in the third game of the second set.
But Williams began to have shaky moments. The first came in the eighth game of the second set when Radwanska got her first break of Williams' serve. After Williams missed a forehand wide, the Centre Court erupted in noise when the second set was evened at 4-4.
And Radwanska broke Williams again to win the second. Williams had a double fault in that game and the final point was a nervous Williams backhand into the net.
When Radwanska, who could have climbed to No. 1 in the world rankings with a victory, held serve to begin the third set, it was the first time the Polish player was ahead in the match.
Williams had two break point chances to take an early lead in the third set. But Radwanska forced Williams into a forehand error to save one and hit a backhand winner to save the second. That was followed by a service winner and a wide Williams backhand, so Radwanska stayed ahead 2-1.
But Williams seemed to get a second wind in the fourth game of the final set, when she held serve with four consecutive aces. That was followed by the first service break in the third set, the most notable shot being a Williams forehand smash that gave her the break point.
Williams consolidated that break and took a 4-2 lead by holding serve at 15. And she broke Radwanska again with an unexpected drop shot during a hard-hitting rally for a 5-2 advantage.
The clinching shot was a backhand winner and her fifth Wimbledon title ties her with her sister, Venus.
“Aggie played so well. That's why she has had such a great career, and so young," Williams said. "You guys should give her another round of applause because she's amazing and she did an amazing job today."
Radwanska will be the new No. 2 player in the world rankings, when Victoria Azarenka, the Australian Open champion, ascends back to No. 1 and Maria Sharapova, the French Open champion, relinquishes the top spot.