The tenets of coordination chemistry enable researchers to design and develop nanostructured materials based on metal–organic frameworks (MOFs). Herein, for the first time, we applied the Schiff base system to MOF derivatives as a strategy for the heteroatom introduction into carbon-based metal oxides toward electrochromic applications. The presented Ni-MOF thin films based on Schiff base ligands were prepared by a facile and economical reductive electrosynthesis approach, facilitating the scalable fabrication of large-size electrochromic films derived from MOFs. After the pyrolysis, the desired N-doped NiO@C (N-C@NiO) films can achieve a high cycling stability (500 cycles with 7% contrast attenuation) and coloration efficiency (80.18 cm2/C) via different pyrolysis procedures. In addition, the one-step fabricated N-C@NiO shows an excellent ability of contrast modulation (68%@580 nm) with merely 3.6% transmittance at the colored state. These improvements in electrochromic properties are attributed to hierarchical porous heterostructures and influenced by the N/C ratio and C–N bonding configuration, indicating that N-C@NiO systems derived from Schiff base MOFs are promising for low-transmittance displays.