Vanadium pentoxide (V 2 O 5 ) films can be easily obtained through the spray pyrolysis technique (SPT), although they are often accompanied by other vanadium oxide phases. The V 2 O 5 phase growth is only observed at low starting solution concentrations and/or at slow deposition flows with high crystalline orientation. These conditions limit the characterization of new V 2 O 5 properties and their industrial application. Sucrose use as reagent in the precursor solution was versatile enough to produce vanadium pentoxide under high flow rates and relatively high starting salt concentrations. In addition, it efficiently randomized the texturing of SPT-deposited samples. Nanostructured and polycrystalline vanadium pentoxides were obtained at salt concentrations ranging from 100 × 10 −3 to 400 × 10 −3 mol•L −1 , at temperatures varying from 265 to 450 °C and a flow rate of 3000 mL•min −1 . Moreover, when it comes to controlling the surface texture of deposited films, one can assume that sucrose is a chelating agent capable of keeping the octahedral coordination of the vanadium complex and favoring further vanadium pentoxide formation.