The [3 + 2] cycloaddition reaction of C 60 with pyridine‐derived hydrazones (acting as dipolar reagents) was successfully conducted resulting in fullerene derivatives 5a , 5b . The compounds were characterized by means of NMR, UV–Vis spectroscopy, and X‐ray crystallography. The electrochemical behavior was also investigated. The fulleropyrazoline 5a exhibits anodically shifted reduction potentials of about 100 mV when compared with those for C 60 , whereas 5b exhibits cathodic shifts relative to pristine C 60 . The complexation reaction of 5b with metallic ions (Zn 2+ , Cd 2+ , and Fe 2+ ) was achieved. Job and Benesi–Hildebrand analysis confirmed the formation of complexes with a molar ratio of 1:1 and binding constants between 2.26 × 10 5 and 1.59 × 10 5 M −1 . Electrochemistry of these complexes showed a marked influence of the metal ion on the reduction potentials. Copyright © 2016 John Wiley & Sons, Ltd.