A Zn(II) coordination polymer {[Zn3(paz)(btc)2(H2O)8]·4H2O}n (noted as ZnPB), where paz = pyrazine, H3btc = trimesic acid, was synthesized and characterized by single‐crystal X‐ray diffraction, elemental analysis, infrared spectroscopy and powder X‐ray diffraction analyses. ZnPB shows a (3,3)‐connected 2D network with a point symbol of (63)2. Hydrogen bonds and π···π interactions connect adjacent 2D network to form a 3D packing structure. This compound exhibits excellent catalytic activity in the reaction of condensation and cyclization of sulfonyl hydrazides with 1,3‐diketones for the synthesis of pyrazoles. This solvent‐free and halogen‐free catalytic system represents an effective economic and environmentally friendly method for the construction of pyrazoles.