China Southern has started flying from Gatwick, meaning the airport is now served by the country’s three major airlines.
China’s largest carrier began twice-weekly flights to Zhengzhou on Tuesday.
The service, using Boeing 787-8 aircraft, is the only direct route between London and the capital of Henan province.
Gatwick, which is also served by Air China and China Eastern, now has 16 flights a week to China, with two daily services to Shanghai already operating.
Aviation development vice president Stephanie Wear said: “The new service to Zhengzhou will enable passengers to not only visit a fantastic city steeped in history and culture, but also visit family and friends, and connect to destinations across China and Asia.”
She added: “China is a hugely important market for us, our passengers, and the regional economy, so it’s fantastic news for London and the southeast to have China’s three major airlines operating from Gatwick for the first time.”
Zhengzhou, which has a population of more than 10 million, is home to the world’s largest iPhone factory.
Gatwick’s planning application to bring its northern runway into regular use was recently accepted for detailed examination by the Planning Inspectorate.