Two classes of unsymmetrical, orthogonally protected bis‐fulleropyrrolidine amino acids have been prepared as models for fullerene‐based peptidomimetics with the carbon sphere inserted into the peptide backbone. Two successive [3+2]cycloadditions of azomethine ylides (thermally generated from formaldehyde and the corresponding orthogonally protected glycino‐amines and ‐acids) to C60 afforded NHFmoc/CO2tBu and NHBoc/CO2Me fulleropyrrolidine couples, offering the possibility of selective deprotection under both acidic and basic conditions. In both classes of unsymmetrical bis‐adducts, the distribution of all the trans (t1–t4) and equatorial (e′ and e″) isomers was quite similar except for the t3 NHBoc/CO2Me compound, which rapidly decomposed during chromatography. All compounds were characterized by UV/Vis, 1H and 13C NMR spectroscopy, and mass spectrometry.