Polymers derived from nickel complexes of salicylaldimines are extensively studied due to their electrochemical, catalytic and sensing properties. However, almost all studies are devoted to the polymers obtained from tetradentate bis(salicylidenaldiminato) complexes, in which the aromatic rings are bound via an imine bridge. Herein we report a first systematic study focused on the polymerization of salicylaldimine nickel complexes without a bridge between the imine fragments. As a result, an impact of the ligand structure on the polymerization ability of the complexes and electrochemical behavior of the polymers obtained thereof was discovered and quantified. An observed phenomenon was rationalized both computationally and experimentally, involving the electrochemical and spectroelectrochemical techniques.