Following the complex-as-a-ligand strategy, self-assembly of W(CN)83- and iron(II) with bidentate nitrogen donor ligand bik (bik = bis(1-methyl-1H-imidazol-2-yl)ketone) ligand affords a cyanide-bridged W2Fe2 molecular square complex HNBu32{W(CN)82Fe(bik)22}·6H2O·CH3OH (1). The complex was characterized by single-crystal X-ray diffraction analyses, (photo)magnetic studies, optical reflectivity, electrochemical studies, and spectroscopic studies. Structural analyses revealed that in the W2Fe2 square motif tungsten(V) and iron(II) centers reside in an alternate corner of the square and are bridged by the cyanide ligands. Complex 1 exhibits thermo-induced spin crossover (SCO) between {WV (S = 1/2)-FeIILS (S = 0)} and {WV (S = 1/2)-FeIIHS (S = 2)} pairs near room temperature and photoinduced spin-state switching with TLIESST = 70 K under light irradiation at low temperature. To the best of our knowledge, 1 represents the first complex containing iron(II) and WV(CN)83- units exhibiting both SCO and photomagnetic effect. © 2021 American Chemical Society.