In an exhilarating first half which saw the Irishman notch his first competitive goals for Killie, the Ayrshire side also scored through the mesmeric David Fernandez and Mehdi Taouil from the spot.
The visitors kept in touch - but only just - through a Gary McDonald strike and a Lee Miller penalty.
Surprisingly, the second half was goalless although there was more likelihood of Killie stretching their lead than Aberdeen retaining their unbeaten record on the road.
While Killie boss Jim Jefferies watched his side bounce back in fine style after back-to-back defeats by both Old Firm clubs, Dons manager Jimmy Calderwood finds himself under a little bit more pressure following the Pittodrie club's poor start to the season.
The competition has its critics but the fans who turned up were treated to six goals in 33 minutes as both sides drove at each other from the first whistle.
In the second minute Sammon raced through on to a David Lilley pass before forcing the ball past Dons' stand-in keeper Bertrand Bossu.
Three minutes later, however, the visitors were level. Midfielder Sone Aluko's 20-yard drive was deflected in to the path of McDonald who steered the ball from 10 yards past Killie goalkeeper Alan Combe and into the corner of the net.
In the 12th minute Killie regained the lead when left-back Jamie Hamill forged his way down the left and swung in a cross to the near post aimed at Sammon.
The ball was blocked by a posse of Dons defenders to Fernandez who, despite the acute angle, drove past Bossu and in low at the far post.
In the 17th minute, after referee Dougie McDonald had been alerted by his assistant Gary Sweeney that Fernandez had been man-handled in the box by Pittodrie skipper Scott Severin, Taouil sent Bossu the wrong way from the spot.
Killie were rampant and the nervous looking Bossu had a decent save from a Craig Bryson drive before Aberdeen raced up the park and won a penalty after Rugby Park defender Frazer Wright brought down Dons striker Darren Mackie.
Miller scored from the spot to reduce the gap back to one goal and the scoring had not finished.
As the home side flooded forward again, midfielder James Fowler picked out Sammon, who all too easily breached the visiting defence before slamming the ball past Bossu.
Aberdeen midfielder Richard Foster then sent a 30-yard shot crashing off the Killie crossbar and, after more escapes at either end, the whole of Rugby Park took a breather when the half-time whistle sounded.
Sammon had picked up an injury and was replaced at the interval by Donovan Simmonds while Lee Mair replaced Pittodrie midfielder Mark Kerr.
McDonald almost pulled a goal back for Aberdeen within a minute of the restart, his shot deflected inches past the post for a corner which Dons stopper Alexander Diamond headed over.
At the other end, Hamill finished a wonderful run across the penalty area by playing a one-two with Bryson and blazing over the bar.
The second half was more sedate but with Aberdeen forced to push forward in order to get back in to the game, play was stretched and the free-flowing home side promised time and again to further increase their lead.
In the 68th minute the impressive Hamill finished another driving run down the left by drawing a fine save from Bossu and moments later, with the Dons defence all at sea, Simmonds hit the post when he should have scored.
A long-range effort from Kilmarnock midfielder Manuel Pascali with 10 minutes remaining was spilled by Bossu but Aberdeen escaped before eventually running out of steam and hope.
The Kilmarnock players deserved and enjoyed their standing ovation at the end.