An unusual, honeycomb-like cadmium-tri-thiocyanate polymeric framework was found in the studied hybrid material of general formula (L²⁺)_n[Cd(SCN)₃]_2n ²ⁿ⁻ (3), where L²⁺ is bis[4-(N-benzylpyridinium)]piperazine dication. The perforated coordination net forms due to a template effect of the organic dications which reside in the holes penetrating the net in a polyrotaxane-like manner. The salt (L²⁺)(SCN)₂·2H₂O (4) was studied for comparison.