The reactions of [Cu(CH₃CN)₄]PF₆ and Cu(ClO₄)₂ with (1-benzyl-1H-1,2,3-triazol-4-yl)(pyridin-2-yl)phenylmethanol (Hpytm) in a 1 : 1 ratio under aerobic conditions afforded [Cu₆(pytm)₆(SiF₆)](SiF₆)₂ (1) and {[Cu₃(pytm)₃(MeOH)(ClO₄)](ClO₄)₂}_n (2), respectively. Single-crystal X-ray crystallography reveals that both compounds contain the trinuclear, six-membered Cu^II cluster, [Cu^II₃(μ₂-κ³-N,O,N′-pytm)₃]³⁺, as a building block. In 1, the two trinuclear clusters sandwich an SiF₆²⁻ anion to form a discrete dimeric hexanuclear structure, whereas in 2 the Cu^II clusters are linked by ClO₄⁻ anions in a one-dimensional polymeric structure. Magnetic susceptibility measurements indicate that a relatively large antiferromagnetic coupling exists in each trinuclear cluster in 1 and 2, with the J values of −48.2(4) cm⁻¹ and −69.2(2) cm⁻¹, respectively. In addition, weak yet non-negligible magnetic interactions between two Cu^II₃ cluster units were observed for both complexes.