Catalytic performance of solid supported monovanadate catalysts toward oxidation of propane is significantly affected by the templating effect of: (1) pretreatment of the solid support with calixarene derivatives before deposition of ammonium vanadate, (2) direct deposition of vanadyl phthalocyanine as the vanadate precursor. This effect is believed to be linked to the accessibility of the active sites, and was studied in comparison with a reference mesoporous support.