[Display omitted] • Two novel A-A type dithienylethene derivatives have been developed. • They showed an efficient solvent-dependent photochromism. • Excellent photoswitching behavior was observed in the PMMA film state. • The DFT calculations further confirmed the above experimental results. Exploring novel dithienylethenes (DTEs) with efficient photochromism has drawn increasing attention in virtue of the potential applications for photoelectric functional materials. In this contribution, we presented two novel acceptor–acceptor (A-A) type DTE derivatives (4a and 4b) by incorporating the diestervinyl moieties with strong electron-withdrawing capacity into two sides of DTE skeleton. The corresponding structures were well confirmed by the NMR (1H and 13C) and HRMS. When irradiated alternately with ultraviolet and visible light, 4a and 4b showed efficient photochromism in toluene, chloroform and DMSO, clearly implying a solvent-dependence feature. Moreover, excellent photoswitching behaviors were also observed in the poly(methyl methacrylate) (PMMA) film. The density functional theory (DFT) calculations suggested that strong Acceptor-Acceptor effect plays a dominative role in the efficient photochromic performance. Hence, this study will provide a useful guidance for developing high-performance DTE derivatives in multi-media. [ABSTRACT FROM AUTHOR]