China claims democratic Taiwan as part of its territory and has never renounced the use of force to bring the self-ruled island under its control.
Ma, of the Beijing-friendly Kuomintang party, oversaw an improvement in cross-strait ties during his 2008-2016 stint in office, culminating in a summit between him and Chinese President Xi Jinping in Singapore in 2015.
But China has intensified pressure on Taipei ever since Ma was succeeded in 2016 by Tsai Ing-wen, who rejects Beijing's claim to the island.
Tensions have further risen since January, when Tsai's deputy Lai Ching-te -- whom Beijing regards as a "dangerous separatist" -- was elected to succeed her.
Speaking to reporters at the airport before his departure, Ma described his trip to China as "a journey of peace and a journey of friendship".
"I hope that when the situation across the Taiwan Strait is tense, we can convey the sentiments of the Taiwanese people that they love peace, hope for cross-strait exchanges and hope to avoid war," he said.
Ma added that he aimed to promote youth exchanges and to "reduce hostility and accumulate goodwill".
Outside the airport, a handful of demonstrators protested against the visit, urging Ma "not to sell out Taiwan".
Last year, Ma made the first visit to China by a current or former Taiwanese leader in more than seven decades in a bid to improve the "cross-strait atmosphere".
On Monday, he said that trip "proved that this method is feasible and we can resolve cross-strait confrontation through building friendship between young people on both sides".
Ma is leading a delegation of 20 Taiwanese students, and will visit tech companies, universities and historical sites in Guangdong and Shaanxi provinces before arriving in Beijing on Sunday.
Asked to comment on Taiwanese media reports that Ma might meet with Xi again during the visit, the former leader's spokesman said it remained to be seen.
"Since we have the opportunity to go to Beijing, former president Ma also hopes to meet old friends. But everything depends on the mainland side's arrangements since we are guests," Hsiao Hsu-tsen told reporters.
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