Edwards, a former UFC champion himself, lost his title to Muhammad last July but the UFC wanted to keep the Birmingham fighter on the London card.
The 33-year-old is expected to be granted a chance to reclaim his title if he wins his next few fight.
American Muhammad upset the odds to beat Edwards in Manchester and defends for the first time.
The 36-year-old is on a 10-fight unbeaten streak, including one no-contest, and said Della Maddalena was stepping out of the “kiddie pool into the deep end of the ocean”.
Della Maddalena has won his last 17 fights, seven of those in the UFC, and this will be his first time challenging for a UFC title.
“I am the best striker in the welterweight division,” said Muhammad. “I am the best grappler, I am the best wrestler, I am the best fighter.
“We’ve seen it. Leon Edwards – he was the next one up. He knocked out Kamaru Usman and I made it look easy. I am going to make it look easy on 10 May. People keep doubting me and I am just going to keep breaking those barriers.”