The Dutch defender was inconsolable after picking up a hamstring injury in Spurs' 2-1 EFL Cup last-16 win over Manchester City on Wednesday, and he will be missing until after the international break.
Cristian Romero also failed to last the full 90 in midweek, but Postecoglou is confident that the Argentine will be OK for Sunday, where he should welcome Radu Dragusin to the backline in Van de Ven's place.
Pedro Porro, Destiny Udogie and Guglielmo Vicario will no doubt start against the Villans too, as should James Maddison and Dejan Kulusevski, who provided assists for both of Spurs' goals against Man City.
Postecoglou has the best kind of midfield dilemma to solve in the deepest role, though, as Pape Sarr doubled Spurs' lead in midweek with a sublime 25-yard finish and has put his name in the hat for a start over Yves Bissouma and Rodrigo Bentancur.
Further forward, Son Heung-min is expected to make his comeback from a hamstring issue on Sunday, so Timo Werner - despite opening his account for the season on Wednesday - will likely be demoted as the Tottenham captain joins forces with Dominic Solanke and Brennan Johnson here.
Tottenham Hotspur possible starting lineup:
Vicario; Porro, Romero, Dragusin, Udogie; Kulusevski, Sarr, Maddison; Johnson, Solanke, Son
Monaco 
Stade Brestois 29 
Bordeaux 
Nimes 
Bayern Munich 
FC Augsburg 
Paris Saint Germain 
Toulouse 
CSKA Moscow 
FC Rostov 
Leicester 
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Valencia 
Betis 
Dynamo Kyiv 
Chornomorets Odesa 
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Inter 
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FC Heidenheim 
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