Venus Williams will also be in action, along with Danish former world No1 Caroline Wozniacki and local hope Marina Erakovic.
Fans will also get to see New Zealand wildcard Jade Lewis, in her first outing in a main draw WTA event.
The previous biggest day in the ASB Classic was probably on the Tuesday of the 2016 event, with Venus Williams, Wozniacki and Ivanovic were in action. But the presence of Serena, and two New Zealanders, takes the event to a new high.
Due to the weather on Monday - which meant only two first round matches were completed - there is also a stacked schedule on the outside courts.
Five singles matches are scheduled for the Grandstand court alone, with fourth seed Barbora Strycova, French Open semifinalist Kiki Bertens and promising Croatian Ana Konjuh.
But - as with yesterday - all is dependent on Auckland's fickle weather.
Today's Play
Centre Court: Starts 12:30 pm
1-S. Williams (US) vs P. Parmentier (FRA)
A. Beck (GER) vs N. Osaka (JPN) to continue
WC-M. Erakovic (NZL) vs 7-J. Ostapenko (LAT)
N. Gibbs (US) vs 3-C. Wozniacki (DEN)
Not Before 6:30 pm
WC-J. Lewis (NZL) vs 2-V. Williams (US) 6-A. Pavlyuchenkova (RUS) vs J. Goerges (GER)
Grandstand: Starts 12:30 pm
4-B. Strycova (CZE) vs Q-B. Stefkova (CZE)
L. Davis (US) vs 5-K. Bertens (NED) 35
Y. Wickmayer (BEL) vs J. Larsson (SWE)
8-A. Konjuh (CRO) vs K. Flipkens (BEL)
N. Broady (GBR) vs D. Kovinic (MNE)
Court 2: Starts 12:30 pm
Q-M. Barthel (GER) vs M. Lucic-Baroni (CRO)
Q-J. Loeb (US) vs M. Brengle (US)
Qualifier vs V. Lepchenko (US)
Not Before 5pm
T. Maria (GER) / N. Melichar (US) vs D. Schuurs (NED) / R. Voracova (CZE)