The reaction of CoCl2 · 6H2O with 6-chloro-2-hydroxypyridine (Hchp) and 1,10-phenanthroline (phen) afforded the complex [Co(chp)2(phen)] (1). Although this complex has been previously reported, it was obtained in this work under mild conditions (in acetonitrile at room temperature) and characterized for the first time by single-crystal X-ray diffraction. The use of Co(F3CCOO)2 · 4H2O under similar conditions yielded a new trinuclear molecular complex [Co3(chp)2(F3CCOO)4(phen)2] (2). According to X-ray diffraction data, the cobalt(II) ions in complexes 1 and 2 are located in an octahedral environment (coordination number CNCo = 6). As an ambidentate ligand, Hchp exhibits different types of coordination modes in the resulting complexes 1 and 2. Additional stabilization of molecules in the crystal is achieved by π-π stacking between aromatic systems of coordinated phen ligands. The cytotoxic activity of 1 and [CoCl2(phen)2] · 1.5MeCN (3) against a panel of human cancer cell lines (SKBR3, HCT116, A549) and normal dermal fibroblasts (HDF) was evaluated using the MTT assay. Complex 3 demonstrated cytotoxic activity against the HCT116 cell line comparable to that of cisplatin, indicating its potential as a promising antitumor agent.