The preparation of novel highly water‐soluble electrostatic complexes from C60‐anchored multi‐armed poly(acrylic acid)s and cationic porphyrin derivatives was demonstrated. The UV‐vis absorption and photoluminescence (PL) of these complexes show that the absorption of soret band exhibits a remarkable red shift and the emission of the Q band indicates an apparent quenching effect in comparison with that of the parent cationic porphyrin. These results imply a remarkable ground state and excited state interaction between the porphyrin ring and the C60 moiety.