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Williams took just 79 minutes to demolish Maria Sharapova 6-2, 6-4 on Centre Court on Thursday, giving the five-time Wimbledon champion her 18th career win in 20 meetings with her bitter rival.
The 33-year-old American will be making her 25th Grand Slam final appearance, and her eighth at Wimbledon, as she chases a 21st major title.
"I got a little nervous because it was the semi-finals and it's a long time since I've been this far at Wimbledon. I'm excited to get through," said Williams, who didn't allow Sharapova a single break point.
"It wasn't easy out there, but when she stepped up her game I was able to step up mine."
Williams' serene progress was in stark contrast to the gritty efforts of the 21-year-old Muguruza, who took just short of two hours to defeat Polish 13th seed Agnieszka Radwanska 6-2, 3-6, 6-3 and become the first Spanish woman in 19 years to reach the Wimbledon final.
Arantxa Sanchez-Vicario was the last Spanish woman to make the final at the All England Club, while Conchita Martinez was the last Spanish champion in 1994.
"I have worked all my life for this, I have no words," said the big-hitting Muguruza, who plans to fly her family into London in time for her first Grand Slam final.
"It was a tough match. Agnieszka has so much experience but I just wanted to keep fighting."
Muguruza, a two-time French Open quarter-finalist, has lost two of her three meetings with Serena and the American is heavily favoured to secure a third success against the world number 20.
But Muguruza, Venezuela-born and Barcelona-raised, can take heart from her stunning French Open second round victory against Serena last year, in which she allowed the American just four games.
Serena, who extended her winning run at Grand Slams to 27 matches and her 2015 record to 38-1, is just one win away from holding all four major titles at the same time -- a feat she last achieved in 2002-03.
She is also within touching distance of becoming the first woman to win the French Open and Wimbledon back to back since she last achieved that difficult double in 2002.
And, adding to the wealth of historic milestones in her sights, Serena remains in the hunt to be the first woman since Steffi Graf in 1988 to win a calendar Grand Slam.
It was another chastening defeat for Sharapova and, although the Russian world number four is due to return to number two in the rankings next week, the latest instalment of their one-sided rivalry provided further proof of the vast gulf in class..
Muguruza, who knocked out fifth seed Caroline Wozniacki and 10th-seeded Angelique Kerber to make the last four, had to endure far more nervy moments before she saw off 2012 Wimbledon runner-up Radwanska.
She saw a 3-1 lead in the second set disappear as the shot-making Radwanska hit back to level the match and then broke in the first game of the final set.
But the Spaniard, who has only one tour title to her name, broke back and then got lucky when Radwanska challenged a ball she believed to be out but replays showed to be on the line.
"I was praying it was on the line," Muguruza said of the challenge which took her to match point.
Had Radwanska not challenged, she would have won the point as the Spaniard had continued playing and hit her next shot out.
"It was 50/50 call on that ball. I decided to challenge. Wasn't really a good decision," Radwanska said.
