Jaroslav Hlinka, Wojtek Wolski and Brett Clark also scored for the Avs while Dustin Penner and Tom Gilbert responded for the Oilers.
Smyth, who left a trail of tears when traded from Edmonton last March before ultimately signing in Colorado, was held off the scoresheet.
It was the first road victory in five tries this season for the Avalanche (5-4-0) while Edmonton lost their six game out of their last seven outings to fall to 3-6-0 and has now lost all five of their games against divisional rivals.
Colorado started the scoring midway through the first as Arnason picked the pocket of Oiler defenceman Denis Grebeshkov and went in on a two-on-one, electing to wire a wrist-shot to the top corner past Edmonton starter Dwayne Roloson.
The Oilers were able to knot the score back up a couple minutes later on an odd man break of their own as rookie Andrew Cogliano fed Penner and his quick shot beat Colorado netminder Peter Budaj.
The sold-out crowd of 16,839 were still cheering that goal when Colorado responded just 23 seconds later as a point shot by Jean-Michael Liles bounced out to Hlinka and he chalked up his first career NHL goal.
The Avalanche took a 3-1 lead into the dressing room with a late first period marker by Wolski. The left wing was able to sneak a puck under a sprawling Roloson, who was trying to cover up the puck with the bottom of his pad.
Edmonton outshot the Avs 12-4 in a mainly uneventful second period.
The Oilers were able to cut the lead back down to one midway through the third as Sam Gagner fed a pass off of Penner's skate to a pinching Gilbert who blasted the puck into the back of the net.
Clark scored an empty-netter with 18 seconds left to salt the game away for Colorado.
Edmonton hosts the Minnesota Wild on Thursday while the Avalanche close out their four-game road trip in Calgary on Friday.
Notes The Oilers honoured Smyth with a video presentation prior to the game. Smyth, who spent 12 years with Edmonton, was given a standing ovation. Not surprisingly the emotional forward was visibly moved. ... The Oilers were without defenceman Joni Pitkanen, out indefinitely with a knee injury suffered in Edmonton's last game against Calgary. Pitkanen will undergo arthroscopic surgery on Friday. Edmonton was already without another key blueliner in Sheldon Souray, still likely gone for three more weeks with a separated shoulder. ... Tonight is the first of eight meetings this season between Edmonton and Colorado. Last year, each team won four times. ... With a first period assist Joe Sakic needs only two more points to become only the eighth player in NHL history to reach 1,600 career points.