The [60]fullerene-initiated “charge-transfer” bulk polymerization reaction of N-vinylcarbazole (NVC) under microwave irradiation (490W) has been demonstrated. In comparison with the C60-initiated polymerization reaction of NVC in the water bath at 70°C, carrying out the polymerization reaction in the microwave oven was found to be advantageous due to the remarkable decrease in the time necessary to carry out reaction, and to the considerable improvement in yield of poly(N-vinylcarbazole). A reasonable polymerization reaction pathway via C60–NVC ion–radical pairs is suggested.