The 23 time Grand Slam victor Serena, playing her first tournament for 14 months following the birth of her child, beat Kiki Bertens of the Netherlands by a 7-6, 7-5 scoreline in her second round match at the Indian Wells Tennis Garden to set up the tie with her older sister and eighth seed Venus.
Venus Williams said of her sister's form in her return to action, "She looked like she never lost a step".
"I really abhor every time we play, but I do enjoy the battle when I'm out there", she continued.
"I'm really happy that I won this first-round match".
They have faced each other repeatedly at the other most significant American tournaments, five times at the United States Open, four times in Key Biscayne, Fla., at the tournament now known as the Miami Open. She won her first service game to love and flexed her muscles early on with a 100mph serve. "I'm just out here on this journey doing the best I can".
Serena, who lifted her 23rd Grand Slam title in Melbourne past year, was then already pregnant with daughter Alexis Olympia, who was born in September. She takes a career head-to-head record over Venus of 17-11 into their third-round clash.
The eighth-seeded Venus beat Romanian Sorana Cirstea 6-3 6-4 in the preceding match.
Her victory was made all the more sweet by her being the returning hero at Indian Wells, a venue she and her sister, Venus, had boycotted until as recently as 2015, after reports of racism against their family and that notorious booing by the crowd in 2001, and by the fact that she gave birth in September.
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"Obviously I wish it was anybody else in the draw, literally anybody, but that's OK. It's just afterwards I don't like it as much".
Also moving into the third round was Caroline Wozniaki, the Danish second seed recording a routine 6-4 6-1 win over Lara Arruabarrena.
In the men's tournament at Indian Wells, Roger Federer's opening match was put on hold as heavy rain swept through the California desert.
The fourth-seeded Elina Svitolina cruised to a 6-4 6-3 win over Mona Barthel.
Defending champion Elena Vesnina of Russian Federation also moved into the third round after she beat American Catherine Bellis 2-6 6-1 6-1.
Fifth-seeded Dominic Thiem fired 10 aces to beat Stefanos Tsitsipas of Greece 6-2, 3-6, 6-3; No. 7 Kevin Anderson defeated Evgeny Donskoy 7-5, 6-4; and No. 12 Tomas Berdych rolled past German Maximilian Marterer 6-1, 6-4 in just over an hour.
Federer, 36, had taken a set from Federico Delbonis 6-3 with the second tied at 2-2 when play was suspended.