Louis van Gaal's side were awfully uninspiring during the game, but The Reds were made to pay for dozens of wasted chances in both halves.
Wayne Rooney's late winner marks the first time he has scored at Anfield in over ten years.
Jordan Henderson, Roberto Firmino, Adam Lallana and James Milner were amongsot those with the best chances of the game, but David De Gea brilliantly denied the odds to keep a clean sheet for Man Utd.
Jurgen Klopp, though not selecting a single scouser, lined his team up with a formidable attacking force and strong defensive structure.
Manchester United, meanwhile, lined up with two defensive midfielders in a 4-2-3-1 formation with Rooney up top.
After a fairly even opening 10 minutes, Liverpool suddenly sprung into life. From the middle of the park, Lucas fantastically pinged a long ball over and through to the advancing and onside Lallana, who put himself into a promising position but his firm header from outside the area was blocked by De Gea.
Subsequently, Blind then failed to obtain the loose ball and possession fell to danger man Firmino on the edge of the box. With De Gea scampering back to his line and no defenders marking him, the Brazilian took a couple of strides to the right but his low drilled shot skimmed past the post.
Moments later - after a brief spell of position from the visitors fizzed out - Firmino's pinpoint volleyed pass found Milner on the right side of Darmian, but the Englishman couldn't keep his shot down and disappointingly blootered over the crossbar.
Often regarded as the biggest match in British football, Marouane Fellani and Lucas emphasised and warranted that substantial label. After the involvement in several tasty tackles, the two holding midfielders collided. Heads together, words exchanged, Mark Clattenburg was forced to intervene as Anfield roared in the heat of battle.
Darmian pioneered one of the few Manchester United attacks, but after running into traffic, Jurgen Klopp's side transferred the pressure back onto the visitors. Firmino pinged another accurate long ball over to Milner on the left this time, who fed the speedy Alberto Moreno the overlap. Approaching the area with pace and intent, he underwhelmed with a poor cross easily cleared by Fellaini.
After half an hour, The Reds, and in-particular Firmino and Henderson, were capitalising on United's disorganization at the back with frequent attacks. Firmino and Lallana linked up outside the area, before puzzling Blind to slide a pass through to Henderson but his shot, to Jurgen Klopp's frustration, sailed over the bar.
Towards the end of the first half, both teams took calculated risks and threw bodies forward. Rooney scampered down the left - before eventually recycling the ball to Darmian - who crossed but failed to find Fellaini and Mignolet claimed possession with ease.
Early in the second half, United enjoyed a promising attacking spell. Rooney skipped past his marker outside the box, then sprayed a pass to Martial on the right. Unbelievably swarmed by dozens of Liverpool shirts, the Frenchman was helplessly squeezed out of position as another decent opportunity fizzled out.
Moments later, Emre Can provoked a brilliant one-legged save from De Gea, before The German saw his shot firmly parried away and Firmino's subsequent rebound lashed away by the goalkeeper's right glove.
Then, after Klopp's men enjoyed a spell in the opposing half, the Red Devils hit back. Borthwick-Jackson, who replaced Young due to injury - crossed low to Rooney - however his attempted shot turned into a backwards flick. Martial pounced, then drove into the box but saw his left-footed shot drift past the far post.
After an uninspiring display for the majority of the game with little glimpses of hope, the irony of Manchester United came to light. Wayne Rooney ended his ten-year wait for a goal at Anfield. From a corner, Marouane Fellaini's header rebounded off the crossbar, and the captain stuck first time on the half-volley past Simon Mignolet to secure a massive victory away from home.