Known affinity of coordination unsaturated manganese(III) phthalocyanines to N-containing bases have been exploited to synthesize photoactive dyads based on manganese(III) 3-trifluorometylphenyl-/3-trifluorometylphenoxy-coated phthalocyanine and pyridine/1′-N-methyl-2′-(pyridin-4-yl)pyrrolidino[3',4':1,2][60]fullerene. The structure and spectral properties of these electron donor-acceptor dyads have been described by chemical thermodynamics/kinetics, UV–vis, IR, 1H NMR spectroscopy, fluorescence, and DFT calculation methods. Comparison of their spectroscopic parameters with those of the corresponding both individual constituents and covalently bonded phthalocyanine–fullerene dyad reveals that there is intramolecular photoinduced electron transfer and related to this prospects in solar energy conversion devices in the case of coordination dyads studied.