The present letter extricates the chemical physics behind non-covalent interaction between fullerenes (C-60 and C-70) and a designed chiral monoporphyrin molecule (1) in toluene. Steady state fluorescence studies on complex formation reveal higher binding constant (K) for C-70/1 complex, i.e., K= 16,020 dm(3) mol(-1), and very good selectivity of binding, viz., K-C70/1/k(C60/1) similar to 10.0. Time-resolved fluorescence study elicits role of static quenching mechanism behind photoexcited decay of 1* in presence of fullerene. Density functional theoretical calculations in vacuo validates the strong complexation between C-70 and 1 and establishes the side-on binding motif of C-70 towards 1 during complexation. (C) 2015 Elsevier B.V. All rights reserved.