China Southern Airlines will deploy its Airbus A380 aircraft on the Guangzhou-Sydney route, starting 27 October.
Sydney airport says the carrier will replace an A330 used on one of the twice daily services.
"This new A380 service will increase Sydney's share of mainland capacity to 56.5%", the airport's chief executive Kerrie Mather says.
Innovata schedules show that the airline is the only operator on the Guangzhou-Sydney route.
China Southern also uses its A380s on routes from Guangzhou to Beijing, Shanghai and Los Angeles.