It will mark the 25th time the sisters have squared off and first since a 2013 semi-final clash in Charleston won by Serena.
While it is a matchup tennis fans always look forward to, for the sisters it is something they could live without.
"I definitely don't like playing her," explained Serena. "I think I've lost to her more than anyone on the tour. Definitely not a fun match.
"She's tough. She has a great serve. She runs every ball down. She has a great backhand. She hits winners off the forehand.
"She does everything well, so it's not an ideal matchup for anyone, to be honest."
Despite the high praise, Serena holds a 14-10 advantage over her older sister in head-to-head meetings and has come out on top in their last five encounters, including the 2009 Wimbledon final.
But the sisterly clashes, which were at one time almost a regular and welcome occurrence on tennis courts across the globe, have become rarer-and-rarer.
In fact, Saturday's meeting will be just the second in the last five years.
Serena, who won the title last year in Toronto, is back in Montreal for the first time in 14 years, while Venus is making her first ever visit to the belle province and now stands as the road block in the way of her sister's title defence.
Both Serena and Wozniacki arrived in Montreal in winning form.
Williams, a three-time champion on the Canadian hard courts, picked up her 61st career title last week at Stanford while Wozniacki was champion in Istanbul. Neither had dropped a set on route to the quarter-finals.
The match served up plenty of intrigue, Williams, the defending champion and current world number one, going against a former number one and former champion, who has her own love affair with the Montreal hard courts where she had built a 9-1 record.
The muscular American was certainly not going to outwork Wozniacki, who is training to run the New York City Marathon in November, but Williams had enough weapons and experience to see off the dangerous Dane.
At 34 Venus continues to prove she remains a force on the court out-lasting Navarro, who at 25 is nearly 10 years her junior.
For the first time since 2010, Venus has reached multiple finals claiming her 45th career title in Dubai.
"She (Venus) is been playing really well. She's in really good form," said Serena. "I definitely feel great when I see her playing so well.
"Obviously not when it's time for me to play her but other than that it always is really good to see her playing really well."
(Reporting by Steve Keating in Toronto, editing by Gene Cherry)
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