The poly(ionic liquid)s (PILs) have attracted a wide range of applications in thermo‐responsive materials, carbon materials, catalysis, porous polymers, separation and absorption materials, and biological field due to their favorable tunability and biological functions. However, the applications of PILs in bio‐scaffold are rarely studied. In the present work, the ionic liquid (IL) monomer (1‐vinyl‐3‐butylimidazolium chloride, [VBIM]Cl) is cross‐linked with other three compounds, respectively, to synthesize three kinds of PILs (PIL1, PIL2, and PIL3). Furthermore, individually cross‐linked PILs are added into gelatin (Gel)/sodium alginate (SA) solution aiming to prepare biological inks (bio‐inks) for 3D printing. The water absorption, degradation rate, and porosity of the bio‐scaffolds are measured to evaluate the physicochemical characteristics, while the PC12 cell line is used to evaluate the biocompatibility of the bio‐scaffolds through cell proliferation. These results demonstrate that the biological activity of the bio‐scaffold can be varied at the tendency of PIL1 < PIL3 < PIL2, providing a potential prospect for the application of PILs in tissue‐engineered bio‐scaffolds.