In recent years, Sn(IV) porphyrins have proven to be excellent choice as photosensitizers for photodynamic therapy. This work reports the synthesis, characterization and photodynamic activity of four high‐valent fluorinated Sn(IV) porphyrins having different numbers of F‐atoms in the peripheral of meso‐phenyl groups viz. (Dichloro)meso‐tetrakis(4‐fluorophenylporphyrinato)stannic(IV), [Sn(IV)FTPP(Cl)2] or Sn1; (Dichloro)meso‐tetrakis(2,4‐difluorophenylporphyrinato)stannic(IV), [Sn(IV)2,4‐FTPP(Cl)2] or Sn2; (Dichloro)meso‐tetrakis(2,6‐difluorophenylporphyrinato)stannic(IV), [Sn(IV)2,6‐FTPP(Cl)2] or Sn3 and (Dichloro)meso‐tetrakis(4‐trifluoromethylphenylporphyrinato)stannic(IV), [Sn(IV)CF3TPP(Cl)2] or Sn4. The solid‐state structure of Sn1 has been determined by single crystal X‐ray diffraction analysis. The increasing number of F‐atoms attached to the meso‐phenyl positions of the porphyrin framework results in increase of their lipophilicity, singlet oxygen quantum yield (ΦΔ) and photocytotoxicity in A549 (human lung adenocarcinoma cells), MCF‐7 and MDA‐MB‐231 (human breast adenocarcinoma) cells. Sn4 predominantly localize in the mitochondria of A549 cells. The light‐induced cell death by the Sn(IV) porphyrins in A549 cells occur primarily via apoptosis.