For the first time, the scope of Fisher esterification has been extended to fullerene derivatives to improve the synthesis of alkyne-functionalized fullerenes (fullerynes) using 1-chloronaphthalene as a solvent and a specially-designed, home-made reactor to promote high yield. The design allows for higher solubility of fullerene derivatives and a continuous azeotropic distillation for the removal of water to drive the reaction to completion with yields >90%. Both fullerynes (Fulleryne01 and Fulleryne02) were found to "click" to polymers, such as azide-functionalized poly(epsilon-caprolactone) (PCL-N(3)), in high efficiency without the need for fractionation. As evidenced by (1)H NMR, (13)C NMR, size exclusion chromatography, and matrix assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, the fullerene polymers thus obtained possess well-defined structure, narrow polydispersity (similar to 1.01 by MALDI-TOF mass spectrometry; similar to 1.03 by size exclusion chromatography), and high fullerene functionality (similar to 100%). They can serve as model compounds for the investigations of polymer structures and dynamics. (C) 2011 Elsevier Ltd. All rights reserved.