Montgomerie, who has now won a European Tour event every year since 1993, moved up three places to come in 11th this week. Langer, who became the first multiple champion of the Volvo Masters Andalucia, jumped 14 spots to No. 17.
Tiger Woods remained comfortably in first place followed by Phil Mickelson and Ernie Els.
Retief Goosen became the seventh player to successfully defend his Order of Merit crown Sunday. He came in first once again on the European Tour money list and occupies the fourth spot in this week's rankings.
David Toms, the 2001 PGA champion, held on to fifth place, while Sergio Garcia and Vijay Singh retained their sixth and seventh spots, respectively.
Padraig Harrington was the only player who could have overtaken Goosen on the Order of Merit, but never mustered a challenge at Valderrama. He finish second on the money list for the second year in a row and held on to No. 8 in the rankings.
Davis Love III and Jim Furyk rounded out the top 10.
Monty took 11th this week as Nick Price, Chris DiMarco and Angel Cabrera each dipped a spot from last week. Justin Leonard moved up one rung to 15th and Michael Campbell climbed two to 16th.
Langer came in 17th, followed by Robert Allenby, who rose one place to 18th. Bob Estes dropped two notches to 19th while Scott Hoch stayed pat at No. 20.
David Duval, the 2001 British Open champion and former World No. 1, fell seven places to No. 22 in the world.