The DBU-promoted three-component coupling reaction of H-phosphonates, [60]fullerene, and alkyl bromides has been developed as a facile and efficient protocol for the one-pot synthesis of various 1,4-(phosphonyl)(organo)[60]fullerenes. This method exhibits high regioselectivity at the 1,4-position on the [60]fullerene core and features a metal-free nature, easy operation, low cost, and a wide range of substrates.