In a match where the home side looked like the visitors and vice-versa, Nacional were unfortunate not to have won by a larger margin.
It was the first time Los Tricolores have won a game on Brazilian soil in the competition since 1971, the year they secured their first of three Libertadores crowns.
The win also meant the Uruguayan side leapfrogged fierce rivals Peñarol in the all-time table of the Copa Libertadores.
After a dominant opening by Nacional they took the lead on the half-hour mark when Dede miss-hit an attempted clearance from Tabare Vuidez's corner, with the ball ending up in the back of the net.
They went into the break with a 1-0 advantage and Vicente Sanchez doubled their lead just a minute into the second-half with a brilliant diving header from a Vuidez cross.
Sanchez then spurned a chance to make it 3-0 when he rounded the Vasco goalkeeper Fernando Prass before blasting the ball over the bar of an empty goal from close range.
Despite dominating the majority of the encounter, Nacional let Vasco back in the game on 73 minutes when Alecsandro was able to pull one back for the Brazilian side.
Vasco then thought they had an equalizer in the 89th minute when Carlos Tenorio had the ball in the back of the net, but the assistant referee correctly ruled out the goal for offside.
Substitute Renato Silva was then sent-off by the Colombian referee Jose Buitrago for protesting the decision from the sidelines.
Nacional held on in the end for the three points and will now travel back to Uruguay to prepare for their second group-stage match against Libertad of Paraguay next Thursday in Montevideo.
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