Energy transfer and electron transfer are both fundamental mechanisms enabling numerous functional materials and applications. While most materials systems employ either energy transfer or electron transfer, the combined effect of energy and electron transfer processes in a single donor/acceptor system remains largely unexplored. Herein, we demonstrated the energy transfer followed by electron transfer (ETET) process in a molecular dyad TPE-NBD. Due to energy transfer, the fluorescence of TPE-NBD was greatly enhanced in non-polar solvents. In contrast, polar solvents activated subsequent electron transfer and markedly quenched the emission of TPE-NBD. Consequently, ETET endows TPE-NBD with significant polarity sensitivities. We expect that employing ETET could generate many functional materials with unprecedented properties, i.e., for single laser powered multicolor fluorescence imaging and sensing.