The reaction between pyrazole (PzH), the N,N-disubstituted cyanamides NCNR₂ (R₂ = Me₂, Et₂, C₄H₈, C₅H₁₀, C₅H₁₀O), and the nickel salts NiX₂·nH₂O (X = NO₃, OTf, ClO₄, Cl, OTs, n = 6; Br, n = 3) affords complexes featuring ligands derived from the Ni^II-mediated cyanamide–pyrazole coupling. The composition of the products and their yields are strongly affected by the choice of NiX₂·nH₂O and a molar ratio between the reactants. The [Ni(PzH)₂{NHC(NR₂)Pz}₂](X)₂ ([1–5](X)₂; R₂ = Me₂1, Et₂2, C₄H₈3, C₅H₁₀4, C₅H₁₀O 5; X = NO₃, OTf – in all combinations, and R₂ = Me₂1 for X = Cl, Br) complexes (named here as bis-chelate complexes), featuring two chelated ligands derived from the cyanamide–pyrazole coupling, were obtained selectively from NiX₂·nH₂O when the molar ratio between the reactants NiX₂ : PzH : NCNR₂ was 1 : 4 : (2.3). By using NiX₂·6H₂O (X = ClO₄, OTs) and with the molar ratio NiX₂ : PzH : NCNR₂ 1 : 3 : (3.5), the pure tris-chelate species [Ni{NHC(NR₂)Pz}₃]X₂ ([6–7](ClO₄)₂, R₂ = C₄H₈6, C₅H₁₀7; [8](OTs)₂, R₂ = Me₂) were isolated. Structurally similar complexes are not formed under the coupling conditions when conventional nitriles NCR (R = Alk; for instance, NCMe) were applied as the nitrile component of the reaction. Quantum-chemical calculations demonstrate that generation of the tris-chelate [Ni{NHC(NR₂)Pz}₃]²⁺ species is thermodynamically driven with the energetic difference 4.6 kcal mol⁻¹ between appropriate bis- and tris-chelate products, while for conventional nitrile derivatives the bis-chelate products are thermodynamically more preferable. The structures of eight complexes, viz. [1](Cl)₂, [1–2](NO₃)₂, [4](NO₃)₂, [1–2](OTf)₂, [3](OTf)₂·Me₂CO, and [9](OTf)₂ were established by single crystal X-ray diffraction.