Blackburn bounced back from an early scare to grab all three points in a lively Lancashire derby.
Robbie Blake had fired Burnley ahead in the first-ever Premier League meeting between the two sides.
But first-half strikes from David Dunn, Franco di Santo and Pascal Chimbonda completed the Rovers return, although there was a late fright as Chris Eagles' effort gave the Clarets hope.
Blackburn were the first to threaten in the fourth minute after El-Hadji Diouf was blocked by Stephen Jordan. Paul Robinson launched the ball forward and Samba took it on his chest only to clear the crossbar with his effort.
Burnley responded and made the breakthrough in the fifth minute through Robbie Blake. He picked up the ball just beyond the halfway line and raced forward as Blackburn backed off.
Blake took advantage to deliver a thunderous strike from 25 yards beyond Robinson that flew into the corner. It was reminiscent of his goal against Manchester United earlier in the campaign and gave Burnley the boost they were looking for.
However, Blackburn equalised in the ninth minute following a flowing move. Pedersen crossed the ball into the area and a clever flick by Franco Di Santo released David Dunn and he scored from close range.
It was an open game and Diouf squandered a good chance six minutes later by sending his shot across the face of the goal after being set up by Steven Nzonzi.
Blackburn went ahead in the 22nd minute when Di Santo took advantage of Graham Alexander's misplaced clearance after goalkeeper Brian Jensen appeared to be impeded by his own defender. Di Santo's goal was his first for the club - and a welcome one at that - after his arrival on loan from Chelsea.
However the way the Argentinian celebrated in front of the visiting supporters did not go down well with referee Chris Foy and he was booked.
Blackburn stepped up the pace and Dunn worked himself into a good position in the 37th minute only to send a soft shot into Jensen's arms. Jensen then had to look alert to take a header from Samba after Dunn had swung in a free-kick from the left four minutes later.
Blackburn extended their lead in the 43rd minute with a splendid goal that cut the visitors apart. Keith Andrews picked out Pedersen on the left and he released Chimbonda on the overlap. The former Tottenham full-back got away from Steven Fletcher and cut into the area before finding the far corner with his effort.
Burnley were anxious to get back into the game and Fletcher dragged a shot wide of the post in the 50th minute after linking up with David Nugent.
Play switched down the other end and the impressive Di Santo skipped away from Steven Caldwell, only for Tyrone Mears to clear for a corner.
There was another scare for Burnley when Jensen misjudged the flight of a long clearance from Robinson only for it go narrowly wide.
The Clarets did grab a glimpse of hope in the dying stages when Eagles slid home past Robinson but Rovers held on to take the honours.