The defending champion, seeking an elusive 22nd grand slam to equal Steffi Graf's open-era record, showed no sign of slowing down against 25-year-old Russian Pavlyuchenkova as they exchanged explosive groundstrokes.
Although Venus, 36, and Serena, 34, are the oldest women in the women's singles, the latter said they did not discuss retirement. They would know when the time came.
"I'm surprised at the longevity of it. That definitely took me by surprise," Serena said after the sisters also completed a 6-4 6-3 doubles victory over Czech pair Andrea Hlavackova and Lucie Hradecka following their singles matches.
"When you're younger and you have a dream and you say it and you believe it, that's one thing. But for it to really happen and to come true, it's just a completely different emotion."
Serena's experience showed on Centre Court against Pavlyuchenkova, who has never gone beyond the quarter-finals at a grand slam.
The American simply bided her time until she was able to seize on moments of weakness from the Russian to ram home her advantage.
She found a chink in her opponent's serving armoury in the ninth game of the first set.
POTENT WEAPON
Pavlyuchenkova, the 21st seed, went for her shots but never found a way to counter the Williams attack. Nerves told again in the same game of the second set, where a series of errors allowed the American to break and then serve for the match.
"She was serving amazingly today," Pavlyuchenkova said. "She was there from the first point to the last."
Serena said she did not know how she had developed such a potent weapon.
"I'm not as tall as all the other players. So it's strange that I have such a strong, hard serve," she said.
"But I have to say what I think really is my game is my mental toughness because just not only to be able to play, to win, but to be able to come back when I'm down.
"Both on the court and after tough losses, just to continue to come back and continue to fight, it's something that takes a lot of tenacity."
The world No.1 -- a position she has held for more than three years -- wrapped up the victory on her second match point with a 123 mph ace for 11 in total.
Venus meanwhile insisted she never stopped believing she could conquer the long road back to the top after the five-time champion reached the Wimbledon semi-finals for the first time in seven years.
Williams reigned supreme at Wimbledon for almost a decade as the American star made it to the final eight times between 2000 and 2009.
But Venus has been a peripheral presence since 2011 when she was diagnosed with Sjogren's syndrome, an illness that causes fatigue and joint pain.
Struggling to deal with the physical and mental damage inflicted by the condition, Williams failed to make the quarter-finals of a Grand Slam for four years.
But she refused to contemplate retirement and gradually learned how to manage her illness alongside reviving her stalled career.
Now, at an age when most of her contemporaries had long since called it quits, the 36-year-old has willed herself back into contention for the eighth Grand Slam crown of her glittering career.
"Retiring is the easy way out. I don't have time for easy. Tennis is just hard," said Venus, who won her last major title in 2008 at Wimbledon.
"It's easy to be afraid. You have to let fear go.
"No matter how things are stacked against you, you just have to believe in yourself. You just have to. There's no way around it.
"The good part is I always felt like I had the game. So you just have to keep working until things fall into place."
A 7-6 (7/5), 6-2 victory over Kazakhstan's Yaroslava Shvedova on Tuesday made Venus the oldest women's Wimbledon semi-finalist since Martina Navratilova in 1994.
On Thursday she faces Australian Open champion Angelique Kerber for a place in her ninth Wimbledon final and first since 2009.