Scholes, who missed United's last and victorious appearance in the final in 1999 through suspension, latched onto a loose ball and drilled a trademark strike beyond Victor Valdes in the 14th minute of a tense semi-final to secure his side's passage into next month's showpiece.
United will now take on either Chelsea or Liverpool in Moscow after edging their way past Barcelona in a nip-and-tuck last four encounter.
The two sides had fought out a goalless first leg at the Camp Nou last week, but United received a blow before kick-off when key duo Wayne Rooney (hip) and Nemanja Vidic (head) were ruled out through injury.
But the Red Devils were much more of an offensive presence on home soil and an energetic performance led from the front by the outstanding Carlos Tevez eventually saw them home.
Scholes struck after United had endured a rocky start, but after that it was the home side who carved out the best opportunities of the night.
Edwin Van der Sar stuck out a strong right hand to divert a Lionel Messi shot following a 20-yard run, while Deco twice lashed rising shots over the crossbar during the first period.
However, Ji-Sung Park should have doubled the advantage midway through the period, but his side-foot effort after arriving onto a Cristiano Ronaldo pull back was inches away from finding the far corner of the net.
Just before the interval, Nani was inches away from diverting a Park cross from close range past Valdes with a glancing header.
Nani also came close to doubling the advantage and killing off the tie in the 53rd minute, but his near-post flick was smothered behind for a corner by the desperate Eric Abidal.
Tevez then stung the palms of Valdes in the 58th minute after playing a superb one-two with Ronaldo before poking a shot straight at the keeper from a tight angle.
An increasingly desperate Barcelona threw on Thierry Henry midway through the half and the former Arsenal striker wasted their best chance of the night after heading Xavi's corner straight at Van der Sar from close range in the 79th minute.
The visitors upped the pressure during a nervous final ten minutes but they failed to find the key to unlock a strong defence superbly marshalled by Rio Ferdinand and Wes Brown.
Ronaldo cut in from the right flank in the dying minutes but dragged a shot from the edge of the area the wrong side of the near post as United rode the storm and secured their place in the first ever all-English final in confident fashion.