Semicarbazones attract attention due to their beneficial biological activities, which are considered to be closely related to their ability to form chelates with metals. Vanadium and copper complexes of salicylaldehyde semicarbazone have been previously reported [1,2]. We currently investigate the interaction of transition metal ions with a similar type ligand, namely with o-vanillin semicarbazone (H2L). The o-vanillin was used for the synthesis of multimetallic assemblies due to variety of bonding geometries of metoxy group. Herein, we report the synthesis and crystal structure of the vanadium(V) and copper(II) complexes, [VO2(HL)]·2H2O (1) and [Cu(HL)(H2O)]2SO4·5H2O (2). Compound 1 crystallizes in the orthorhombic space group P212121, a=5.8870(3), b=13.7731(6), c=16.101(1) Å, V=1305.5(1) Å3. In compound 1 vanadium ion is in a distorted square-pyramidal environment. Monodeprotonated tridentate ligand coordinates to V(V) through azomethine nitrogen atom, carbonyl, and phenol oxygen atoms. Two oxo-ligands complete square-pyramidal surrounding of metal (Fig. 1). In the crystal, complexes are connected directly by weak N–H …O hydrogen bond and via go-between solvent water molecules. Compound 2 crystallizes in the triclinic space group P-1, a=6.6163(4), b=11.005(1), c=20.128(2) Å, α=87.432(9), β=87.530(6), γ=82.494(8)^o, V=.1450.5(2) Å3. The asymmetric part of unit cell 2 contains two similar single-charged cationic complexes [Cu(HL)(H2O)]+, sulfate anion, and five water molecules. In both cations, Cu(II) have a square planar surrounding. Three coordination sites occupy ONO donor atoms of HL- and forth one water molecule (Fig. 2). In crystal, cationic complexes form centrosymmetric dimmers due to couple of N–H…O H-bonds between amide fragments. The surrounding of such dimmer differs for two symmetry independent complex.