Herein, we report the synthesis of new tetraphenylethylene derivatives that feature electron-donating (methoxy) and -accepting (dicyanomethane) groups as AIE-active molecules with tunable emission colors. The crystal structures of compounds and are described and the intermolecular interactions within their crystals agree with the observation that they exhibit strong solid-state emission. Compounds exhibit typical AIE behavior and their emission maxima are red-shifted in the order: <<<. Such red-shifts are ascribed to the fact that intramolecular interactions between the electron donor and the electron acceptor become stronger with increasing number of methoxy groups. The solid-state emission colors of compounds are successfully tuned from yellow-green to red. Compound shows AIE behavior, but its emission is only slightly enhanced after aggregation and its solid shows a low quantum yield. Furthermore, microplates of compound exhibit 2D optical-waveguide behavior.