Muller, 41, currently sits second in the driver's championship but the Frenchman is reeling in Huff, who has led the way throughout the season to date.
Three victories in the past four races has helped Muller close the gap and putting his car on pole for Sunday's opening race at Circuit Ricardo Tormo gives him the perfect opportunity to further dent Huff's six point lead.
Despite topping the times in the two practice sessions and claiming his third consecutive pole position Muller will be weary that Huff's threat as the Briton will line up alongside him on the grid after recording a time 0.456 seconds slower than Muller's best effort of one minute 42.649 seconds.
SUNRED duo Gabriele Tarquini of Italy and Portugal's Tiago Monteiro have locked out the second row while the third Chevrolet driver, Alain Menu, is down in sixth behind BMW's Dutch driver Tom Coronel.
Norbert Michelisz, Javier Villa, Franz Engstler and Michel Nykjaer rounded out the top 10.