The victims included 24 Chinese tourists, and a driver and a tour guide from Taiwan, Xinhua news agency quoted Taiwan authorities as saying.
There were no survivors in the bus which bellowed smoke as it crashed into an outer lane barrier on the highway and caught fire.
The tour bus had a record of five traffic violations in six years of service, the authorities said.
A probe into the cause of the accident was underway, traffic police said.
Taiwan's mainland affairs authority said it would do its utmost to handle issues, including the relatives' visits.
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