How to efficiently design and synthesize multifunctional molecules is particularly challenging. In this presentation, we devote to constructing a kind of simple structures with composite functionalities through straightforward preparation. Starting from common commercially available materials, the titled cis/trans-tetraarylethenes can be conveniently obtained by a one-pot process under mild conditions. The different configurations were confirmed by 1H NMR and single crystal data analysis. The trans-tetraarylethenes could be converted into cis-forms not only by photoirradiation but also by microwave irradiation, which provided us a new choice for isomeric conversion, especially in relation to light sensitivity. Results show that all the hybrid cis/trans-isomers performed switchable fluorescence and reversible photochromism in solution, PMMA film, solid powder, and single crystal. Moreover, these hybrid tetraarylethenes could be utilized as photoswitchable media to tune the behavior of aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ). These versatile properties are favorable for the potential applications in fluorescent photoswitches, nondestructive readout, and logic gates. We hope that our design strategy could provide a new protocol for constructing a kind of multifunctional molecules based some simple structure and convenient synthetic procedures.