The reaction of CoBr2, KNCSe and 2-methyl-pyridine N-oxide (C6H7NO) in ethanol leads to the formation of crystals of [Co(NCSe)2(C6H7NO)3] (1) and [Co(NCSe)2(C6H7NO)4] (2) from the same reaction mixture. The asymmetric unit of 1 is built up of one CoII cation, two NCSe- iso-seleno-cyanate anions and three 2-methyl-pyridine N-oxide coligands, with all atoms located on general positions. The asymmetric unit of 2 consists of two cobalt cations, four iso-seleno-canate anions and eight 2-methyl-pyridine N-oxide coligands in general positions, because two crystallographically independent complexes are present. In compound 1, the CoII cations are fivefold coordinated to two terminally N-bonded anionic ligands and three 2-methyl-pyridine N-oxide coligands within a slightly distorted trigonal-bipyramidal coordination, forming discrete complexes with the O atoms occupying the equatorial sites. In compound 2, each of the two complexes is coordinated to two terminally N-bonded iso-seleno-cyanate anions and four 2-methyl-pyridine N-oxide coligands within a slightly distorted cis-CoN2O4 octa-hedral coordination geometry. In the crystal structures of 1 and 2, the complexes are linked by weak C-H⋯Se and C-H⋯O contacts. Powder X-ray diffraction reveals that neither of the two compounds were obtained as a pure crystalline phase.