Xi arrived in PNG on Thursday for a state visit with much fanfare including China-style giant billboards of the Chinese leader.
He has also held his own meeting with PNG and the seven other Pacific leaders that have diplomatic relations with China: Fiji, Cook Islands, Samoa, Tonga, Vanuatu, Federated States of Micronesia and Niue.
Ardern and the Apec leaders are scheduled to meet them too, before a gala dinner.
Xi announced the start of free trade talks with Papua New Guinea.
Xi reportedly extended China's loans to PNG, and approved a mining project worth over $1 billion.
Several other countries are reportedly set to unveil further development assistance to PNG in a bid to counter China's influence.
The Australian reported on Saturday that Australia, the United States, Japan, South Korea and New Zealand will co-operate on a major energy and internet plan.