The present paper reports a detailed photophysical investigation on the supramolecular interactions of a functionalised fullerene, namely [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₀BM), with a designed monoporphyrin, [bis(4-hydroxyseselinyl)porphyrin] (1), in toluene and 1,2-dichlorobenzene (DCB). The values of the binding constant (K) for the PC70BM-1 systemmeasured by steady-state fluorescence investigation in toluene (KPCBM-1 (toluene)) and DCB (KPCBM-1 (DCB)) are estimated to be 15,085 dm3 mol⁻¹ and 6700 dm3 mol⁻¹, respectively. A moderate value of selectivity (K) is observed for the PC₇₀BM-1 system in toluene and DCB (K_PC70BM-1 (Toluene)/K_{PC70BM-1 (DCB)} ~2.25) due to a solvophobic effect. Life time measurements proved that photo-excited 1⁎ undergoes decay in the presence of PC70BM in toluene and DCB as a result of static quenching. Hybrid-density functional theory (DFT) calculations predicted the geometric structure of PC70BM-1 system in vacuo and established the electronic redistribution between PC₇₀BM and 1 in the PC₇₀BM-1 system with the help of molecular orbital, molecular electrostatic potential map, and multipole bond moment calculations. Transient-absorption measurements established that binding interactions overcome both energy and/or electron-transfer process(es) during non-covalent interactions between PC₇₀BM and 1 in solution.