Two new inorganic–organic hybrid materials – [{M(C 5 H 5 N) 4 } 2 ]V 4 O 12 (M=Cu, 1; M=Co, 2) have been synthesized and characterized by spectroscopic methods, X-ray powder diffraction, thermogravimetry, magnetometry and complete single crystal structure analysis. The structures of 1–2 are comprised of layers containing centrosymmetric {V 4 O 12 } rings connected to {M(C 5 H 5 N) 4 } units by V–O–M bridges (M=Cu, 1; M=Co, 2). The layers are parallel to the (101) crystal planes and there are pyridine stacking interactions between layers. The effective magnetic moment, μ eff , values for 1 and 2 are 1.9μ B and 3.9μ B , respectively, indicating some orbital contributions in each case. Both compounds exhibit Curie–Weiss magnetic behavior over the entire range above the critical temperature.