Vanadium-titanium catalysts modified with phosphorus additives (1-15 wt.% of P2O5) have been studied in methylpyrazine ammoxidation. Introduction of high amounts of the additive (greater than or equal to 10 wt.% of P2O5) results in a decrease in activity and selectivity of the catalysts due to formation of low active phase - a ternary compound with the component ratio V : P : Ti approximate to 1 : 1 : 1 with only one type of slightly distorted tetrahedral vanadium (5+) bound via oxygen to phosphorus (5+). The nature of the active sites of the samples modified with 1-5 wt.% of P2O5, similarly to that in the V-Ti-O catalyst, was found to include the V5+ cations strongly bound with TiO2 and located in the significantly distorted octahedral oxygen environment.