The move comes as the small-group adventure company announces structural changes to support its trade sales growth across the UK.
Baines, who has worked at Explore for nearly four years, said: "We already have a fantastic relationship with travel agents in the UK.
"As we move into 2023 these changes herald exciting times at Explore, and I look forward to leading our agency sales team into this next phase of growth."
Meanwhile, Explore director of sales Ben Ittensohn will be relocating to Brisbane where he will take on a broader, more global role from January.
He said: "The UK is a key market for us, and our trade partnerships are absolutely crucial to Explore’s continued growth.
"These changes will not only strengthen the team but also help deliver on our overall trade sales strategy and secure our growth ambitions for the business."