Great efforts have been devoted to achieving efficient Si-based light-emitting devices. Here we report new light-emitting devices fabricated with Tb2O3 on Si substrates. Intense green electroluminescence was observed, with a turn-on voltage of about 8 V. The green emission is attributed to the characteristic transitions of Tb3+ ions in Tb2O3. The electroluminescence mechanisms of the Tb2O3 light-emitting devices are discussed. In addition, visible and near infrared electroluminescence was observed in rare-earth (Eu3+, Sm3+ and Yb3+) doped Tb2O3 light-emitting devices.