With the assistance of microwave irradiation, greenish-yellow luminescent graphene quantum dots (gGQDs) with a quantum yield (QY) up to 11.7% are successfully prepared via cleaving graphene oxide (GO) under acid conditions. The cleaving and reduction processes are accomplished simultaneously using microwave treatment without additional reducing agent. When the gGQDs are further reduced with NaBH4, bright blue luminescent graphene quantum dots (bGQDs) are obtained with a QY as high as 22.9%. Both GQDs show well-known excitation-dependent PL behavior, which could be ascribed to the transition from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) with a carbene-like triplet ground state. Electrochemiluminescence (ECL) is observed from the graphene quantum dots for the first time, suggesting promising applications in ECL biosensing and imaging. The ECL mechanism is investigated in detail. Furthermore, a novel sensor for Cd2+ is proposed based on Cd2+ induced ECL quenching with cysteine (Cys) as the masking agent.