The world number 108 was selected ahead of higher-ranked Steve Darcis by captain Johan Van Herck and will face world number two Murray in Friday's second singles.
It could be a ploy by Van Herck to keep Darcis fresh for Saturday's doubles and a potential fifth-rubber decider on Sunday against Britain's number two player.
The 27-year-old Bemelmans believes that, despite many thinking he will be a sacrificial lamb against Murray who has won all his six singles rubbers in leading Britain to the final, he can cause the Scot problems.
"This will be the first confrontation I've had with Murray, match or practice, so it's going to be new for him as well," said the Belgian who last won a Davis Cup singles in 2013 against Israel's Dudi Sela.
"I think I probably know him better, how he plays, than him me. Maybe that's a slight advantage there but I will be well prepared and I'm looking forward to tomorrow.
"We've discussed tactics already and I know what to do to make it as hard as possible and, who knows?, to beat him. It's clear I have to bring my very best tennis," added Bemelmans.
His selection was unexpected, especially as Darcis won the decisive fifth rubber against Argentina in the semi-finals and has a 17-8 record in Davis Cup singles.
Darcis will play Saturday's doubles with Kimmer Coppejans and could possibly come into contention again should the final go to a fifth rubber on Sunday.
"Of course I'm disappointed, I was ready to play and felt good, but Johan had a choice to make and I respect the choice. Ruben has had a good week and is confident," he said.
"It could be a long weekend and hopefully they'll need me Sunday and I will be ready."
Van Herck said his side must get off to a good start on Friday when David Goffin faces British debutant Kyle Edmund.
"It will be important to have a winning start and then after that we'll see," he said. "That would put a little more pressure on Andy.
"Friday night we will sit down and see what the score is and then make decisions for the doubles."
(Editing by Tony Jimenez)
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