Both teams had missed out on League action a week ago thanks to the cold weather but Kilmarnock knew the three points would see them consolidate their position in seventh.
The home side were looking to jump above the visitors and replace them in that spot.
Both sides both created some good chances in the opening ten minutes. Killie's Donovan Simmonds forced Well keeper Graeme Smith to make a couple of fine saves while at the other end the Steelmen failed to test Alan Combe with both John Sutton and Chris Porter firing over after some excellent link-up play.
After the opening flurry the game developed into a midfield stalemate with neither side taking control and chances were therefore at a premium.
It took a set-piece to break the deadlock in the 35th minute after Well had appeared to have cleared any danger when Steven Saunders blocked a Simmonds shot for a corner.
However, the Well defence was caught napping from the corner when Manuel Pascali was given the freedom of the six-yard box to head Gavin Skelton's cross into the back of the net.
The goal stung Motherwell into a response but once again they struggled to test Combe with Sutton firing wide and Porter heading over before Steven Hammell's long-range shot was saved.
The keepers were called into action early in the second half with Graeme Smith saving at full length from a Skelton volley while Combe held a 22-yard effort from Stephen Hughes.
Just before the hour mark Combe was tested to the full as he got a fingertip to the ball to deflect a blistering angled drive from Porter on to the crossbar. Minutes later the keeper denied the Englishman again as he blocked at his feet only six yards from goal.
Killie sealed the game with 13 minutes left when a poor clearance fell to Jamie Hamill whose first-time ball sent Allan Russell clear. The striker had all the time in the world to fire an angled drive low past Graeme Smith to register his first goal for the club.