It connects Asia's financial hub, Hong Kong, with the southern mainland city of Zhuhai and the gambling enclave of Macau, across the waters of the Pearl River Estuary with a snaking road bridge and underwater tunnel.
It will reduce travel time between Hong Kong and Zhuhai from four hours to just 45 minutes.
"I think this bridge will bring great convenience to the whole area of Zhuhai, Hong Kong and Macao, and promote the economic development of the whole area of the Pearl River Delta", resident Dang Zheiliang told AFP.
"I declare the Hong Kong-Zhuhai-Macau bridge officially open", Xi said as digital fireworks exploded on a screen behind him in an indoor ceremony, before leaving the stage immediately.
The construction of this bridge started in 2009 and has been marred by several delays.
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Most drivers will have to park at the Hong Kong port, switching to a shuttle bus or special hire cars once they are through immigration.
He said the bridge demonstrates China's engineering capabilities.
Han, Beijing's man in-charge of regional economic integration, said that the 55-km-long bridge could facilitate the development of "one country, two systems", a framework that allows Hong Kong and Macau a certain degree of autonomy.
It also includes a 6.7 km submerged tunnel to help it avoid the busy shipping paths over the Pearl River Delta. Among the guests present included the leaders of Hong Kong and Macau, Carrie Lam and Fernando Chui, and Guangdong Party Secretary Li Xi. That line has vastly decreased travel times but also raised concerns about Beijing's growing influence because mainland Chinese law applies within part of the line's Hong Kong terminus.
A government-commissioned study from 2016 estimated that 29,100 vehicles would use the bridge daily, by 2030, which was 12 per cent down from a report written in 2008.