It was the Dutchman's first final appearance this Premier League season, but the seven-time champion was immediately broken by Littler - looking for his third nightly win.
The defending champion was immediately broken back by MVG before Littler hit the stunning nine-darter via a tremendous double 15 finish in the fourth leg.
Van Gerwen was not to be deterred, responding with 180s galore to take the next two legs to level the match at 3-3 as a spectacular scrap began to unfold.
A big bull finish put Littler back in charge of the contest against the throw, but Van Gerwen again rallied to make it 4-4.
With both players comfortable averaging over 105, MVG missed a dart to take the lead in the match, which proved costly as Littler capitalised and eventually methodically threw out for the win.
Littler threw 10 180s to Van Gerwen's four, while Littler averaged 112.5 to Van Gerwen's 101.4.
It leaves Littler six points clear of Luke Humphries in the table.
"I have been playing very well," Littler told Sky Sports.
"I have not picked my darts up since last Thursday - I had a week off to chill. But to come here and win and be six points clear, I am comfortable.
"All players have to have a rest and after the performance tonight, I will have another week off!"
Dobey bounces Bunting, Voltage sparkles
Chris Dobey got his campaign back up and running with a much-needed 6-2 win over rock-bottom Stephen Bunting. A focused Van Gerwen toppled old foe and world number one Luke Humphries early doors with a 6-4 triumph, and Littler continued his fine form against Nathan Aspinall with a comfortable 6-3 victory.
Rob Cross then disappointed the rowdy home fans after dispatching Welshman Gerwyn Price in a 6-5 thriller, with Cross landing an excellent big fish to seal the deal in stunning style in the last of the opening matches.
Price had fought from three sets down to take the match to a deciding leg but was outdone at the final hurdle by the English party pooper.
However, the buzz for Voltage was to be short-lived as he was soon on the receiving end of a Luke Littler special, succumbing 6-2 to the 108-averaging 18-year-old in the semi-finals.
Cross fought back from three sets down to make it 3-2 but soon hit a Littler wall, ultimately helpless as the youngster raced to a decisive victory via a tidy 120 finish, guaranteeing Littler's place at the top of the table going into the next round even prior to facing the Green Machine in the final.
MVG meanwhile dismantled Dobey 6-1 without breaking much of a sweat on his way to the final with Littler.
The Premier League drama continues with Night Eight taking place next Thursday at the Utilita Arena in Newcastle.