New unsymmetric dinucleating pyrazolate ligands with different chelating side arms in the 3‐ and 5‐positions of the heterocycle have been prepared. These ligands provide a “soft” P∩N site and either an adjacent “N3” (HLa) or “N2S2” (HLb) coordination pocket, and they have been employed to build homo‐ and heterobimetallic complexes featuring various types of asymmetry. Both La and Lb form the mixed‐spin dinickel(II) chloride systems 4 and 5, respectively, which in the former case dimerizes via Cl bridges to give a tetranuclear compound. In the heterobimetallic complex 6 the PdII is specifically housed within the P∩N compartment. All new complexes have been characterized by X‐ray crystallography, and conformational and electronic coupling between the two metal ions of the dinuclear scaffolds have been analyzed.