We report on the site-selective synthesis of PCBM-like fullerene site-isomers, where the elusive -site-isomers are, for the first time, the major product in a (cyclo)addition chemical reaction involving fullerene. The reaction involves an straightforward cyclopropanation of fullerene from sulfonium salts, affording a mixture of and site-isomers in good yields. Amazingly, the preference for the - or -site-isomer can be efficiently controlled by means of the solvent polarity! DFT theoretical calculations (DMF and toluene) nicely predict that, although the formation of the -adduct is, as expected, thermodynamically favored, the selectivity of the process is determined by the energy difference of the respective transition states. Furthermore, the employ of or/and site-isomers, as pure materials or as a mixture of them, used as templating agent, has been evaluated in perovskite solar cells. The positive influence of the fullerenes by passivating the voids/pin-holes and/or deep slits, is reflected in highly efficient and stable bulk heterojunction perovskite solar cells, whose performance (around 20%) is slightly but consistently depending on the isomeric fullerene composition. These experimental findings pave the way to investigate a new reactivity on C-70 and to explore the properties of the less-known -derivatives.