Ternary and polynary phosphates of transition metals offer various chemical and structural properties that make them interesting as catalyst materials for the selective oxidation of light alkanes. Redox potentials, oxygen decomposition pressures, acid-base behavior, and structural chemistry of anhydrous transition metal phosphates may be varied over a wide range. Thus, for selective oxidation reactions of various light hydrocarbons C, (1 <= n <= 4) suitable ternary or polynary vanadium phosphates were found. In this contribution, our recent, results concerning synthesis, crystallographic characterization and catalytic properties of novell ternary and polynary vanadium(IV) phosphates [((MV3O3)-V-III-O-IV(PO4)(3) and M-III((VO)-O-IV) (P2O7), (M-III: V, Cr, Fe), (MV2O2)-V-II-O-IV(PO4)(2) (M-II: Co, Ni, Cu), and Fe(II)Feu(III)((VO)-O-IV)(PO4)(P2O7)] in the selective oxidation of n-butane and 1-butene to maleic acid anhydride are summarized.