The 25/1 shot was in full control of the race after around three quarters of the distance and with an excellent jumping display finished five lengths ahead of Baltzhazar King who was well-backed.
Double Seven, the 10/1 joint favourite who was ridden by champion jokey Tony McCoy, managed third place. Rocky Creek edged Chance Du Roy by a short head to the fifth spot.
This was the second consecutive year that a non-favourite won the Aintree marathon, with Auroras Encore winning after odds of 66/1 in 2013. Sky Bet commentator Michael Shinners said: "The place bets could have been better for us with Double Seven third and Rocky Creek coming fifth, but despite being popular ante-post, Pineau De Re was quite friendless on the day. His win sparked some celebrations on our trading desk.The icing on the cake was that surprisingly all jockeys and horses managed to return home unharmed."
Rory Jiwani from Stan James said: "A year after Auroras Encore, it was another super result for bookies in the Grand National.AP McCoy's Double Seven was by far our biggest loser and had us scared for a moment but Pineau De Re was a superb result for us. He ran a great race at Cheltenham and when jockey Leighton Aspell pushed him out after the last jump, there was going to be only one winner on a day to remember for his trainer Dr Richard Newland."
"Our joy was slightly tempered by some well-backed horses making the frame like Balthazar King and Double Seven. Paying out on each-way bets for Rocky Creek who was fifth, took its toll on us but we can’t complain and this has put us up for the week."
David Williams from Ladbrokes' stated that it had been an "..outstanding day for bookies.We were staring down the barrel with so many backers for Double Seven and Teaforthree but in the end we've absolutely no complaints with who one. It kind off slipped off the radar and although bookmaker shops were full before the race they'll definitely be quieter with the shorter queues for winnings."
The winner managed a high of 44 in Betfair's in-running exchange, with runner-up Balthazar King trading at 3.2 at one point.
The start was delayed due to Battle Group refusing to start and eventually he didn’t take part in the race, for which several firms have vowed to refund punters.