The American star started her campaign in Melbourne in style, needing just 58 minutes to cruise past Potapova 6-0, 6-3.
Williams was in dominant form from the outset at Rod Laver Arena as she opened her bid to tie Margaret Court’s record of 24 major titles.
The 38-year-old Williams is now 19-0 in Australian Open first-round matches. She will face Tamara Zidansek or Han Na-lae in Round 2.
AUSTRALIAN OPEN: Craig O’Shannessy says data, AI the future of tennis
Williams was flawless in the first set against her teenage Russian foe, hitting 10 winners and taking the opener in just 19 minutes. Potapova improved in the second set and even broke for a 2-1 lead before Williams responded.
Williams grabbed a decisive break in the eighth game when Potapova sent a forehand into the net, and then completed her victory soon after.