The aim of this article is to study the extractive-catalytic oxidative desulfurization (ECODS) of the model oil containing several model S-containing compounds as well as N-containing compound using a heterogeneous vanadium substituted Dawson-type polyoxometalate catalyst under atmospheric pressure and temperature lower than 100 degrees C. The catalyst was prepared by ion exchange with alkyl ammonium derivatives covalently anchored to silica gel. The potential of this methodology was illustrated by oxidation of 100% quinoline and 80% of total sulfur in model oil containing 500 ppmw sulfur and 70% of total sulfur in model oil 1500 ppmw in less than 30 min of reaction, in the absence of solvent. However, when acetonitrile was employed as an extractive solvent, the desulfurization was increased considerably. Under the reaction conditions, activated catalyst and acetonitrile, solvent to oil ratio 1: 6, could remove approximately 100% of quinoline, 95% of sulfur from 500-ppmw model oil, 87% of sulfur from 1500-ppmw model oil in less than 30 min. The catalyst is very active in ECODS and can be reused fifth times from 500-ppmw model oil and third times from 1500-ppmw model oil without an important decrease in activity. The ECODS could remove 83% of total sulfur from 1235-ppmw-S real diesel.