Paul Heffernan had the first real chance of the game after eight minutes, but he could only put his effort wide of the post.
Heffernan had another chance to give the away side the lead on 14 minutes, but he hit his strike straight at the goalkeeper.
Despite the early pressure from Hibs, it was Motherwell who took the lead on 22 minues when Stephen McManus headed home from a corner to make it 1-0.
Henri Anier came close to doubling the home side's advantage on 32 minutes, but his effort from distance was just tipped wide by the goalkeeper.
Anier had a huge chance again on 39 minutes from a long ball, but the striker managed to get the ball caught under his feet, allowing the defenders to clear.
Lionel Ainsworth had a chance inside the box three minutes into the second half, but ended up dragging his shot past the post.
Hibs began to get on top as the game progressed to the later stages, though they struggled to create any clear-cut chances.
Motherwell were reduced to 10 men on 86 minutes when Shaun Hutchinson was shown a second yellow for clearly denying a goal-scoring opportunity.
James Collins had a good chance to equalise on 90 minutes, but the striker fired wide of the mark.