"We hope to help ease cross-strait tensions to ensure people's wellbeing ... to do what the government does not do and cannot do," Kuomintang (KMT) party vice-chairman PK Chiang, who headed the delegation, said on Monday.
"We will also discuss bilateral issues such as the opening of direct transport links and better protection of Taiwanese businessmen in China," Chiang said before departing with the 30-strong mission.
The delegation will fly to the southern city of Guangzhou, where it will pay homage on Tuesday to 72 KMT martyrs who died overthrowing the Qing Dynasty and founding the Republic of China in 1912.
They are scheduled to visit Nanjing on Wednesday to pay respects to Sun Yat-sen, the founding father of the republic, before flying to Beijing where they will meet high-ranking officials in charge of Taiwan affairs on Thursday.
The China Times said Jia Qingling, a political bureau member and deputy head of the central Taiwan Affairs Office, was to meet the KMT group on Thursday.
"The lingering cross-strait tensions must be eased and to do so, efforts must be taken"
Observers said the trip, the first official visit by the KMT to the mainland since it was defeated by communist forces in 1949 and fled to the island of Taiwan, was a prelude to a mainland visit by party leader Lien Chan.
The KMT has called for friendly ties with Beijing while Taiwan's ruling Democratic Progressive Party (DPP) favours declaring the island independent.
"The lingering cross-strait tensions must be eased and to do so, efforts must be taken ... the KMT would like to take an active step," Lien said on Sunday, a day after about 275,000 people in Taiwan took to the streets to protest against China's new anti-secession law.
The law passed this month authorises the use of force against Taiwan if it moves towards formal independence.
Taiwanese authorities have slammed it as tantamount to giving the Chinese military a blank cheque to invade the island, leaving people in constant fear.
The two sides have been governed separately since the 1949 split, but Beijing still considers the island part of its territory awaiting reunification - by force if necessary.