A series of cupric chloride complexes with 1-methyl-5-R-tetrazole ligands, where R = NH 2 , t-Bu, Ph, MeS, CH[dbnd]CH 2 , MeSO 2 , were synthesized by interaction of CuCl 2 ·2H 2 O with the above ligands L NH 2 , L tBu , L Ph , L MeS , L Vin , and L MeSO 2 , respectively. The obtained complexes [Cu(L NH 2 ) 3 Cl 2 ]·H 2 O (1), [Cu(L tBu ) 2 Cl 2 ] (2), [Cu(L Ph ) 2 Cl 2 ] (3), [Cu(L MeS ) 2 Cl 2 ] (4), [Cu(L Vin )Cl 2 ] n (5), and [Cu(L MeSO 2 )(H 2 O)Cl 2 ] n (6) were characterized by single crystal X-ray analysis. The effect of C ⁵ -substituent on coordination modes of tetrazole ligands and structural motifs of complexes was observed. Complexes 1–4 are mononuclear, with the tetrazole ring N ⁴ coordination. Complex 5 presents 1D coordination polymer, formed at the expense of triple bridge between two neighboring copper(II) cations (double chlorido bridge and the tetrazole ring N ³ ,N ⁴ -bridge). In 6, being also 1D coordination polymer, coordination chains are composed of alternating Cu(L MeSO 2 ) 2 and Cu(H 2 O) 2 fragments linked by double chlorido bridges. Ligand L MeSO 2 shows N ³ coordination, being rare among 1,5-disubstituted tetrazoles. The influence of the nature of C ⁵ substituents on coordination features of the obtained complexes is discussed by using quantum-chemical calculations of the electronic structure and basicity of the ligands.