Four novel photochromic dithienylethenes compounds, 1,2-bis[2-methyl-5(p-fluorophenyl)-3-thienyl]perfluorocyclo-pentene (1a), 1,2-bis[2-methyl-5(p-ethoxyphenyl)-3-thienyl]perfluorocyclopentene (2a), 1,2-bis[2-methyl-5(p-N,N-dimethylaminophenyl)-3-thienyl]perfluorocyclopentene (3a) and 1,2-bis(2-methyl-5-naphthalene-3-thienyl)perfluorocyclopentene (4a) were synthesized. Their optoelectronic properties, such as photochromism in solution as well as in PMMA amorphous, fluorescence and electrochemistry properties were systematically investigated. These dithienylethenes have shown good photochromic behavior both in solution and in PMMA amorphous film. All of them exhibited relatively strong fluorescence. With the increase of their concentration in a THF solution, their fluorescence spectra showed a bathochromic shift. The irreversible anodic oxidation of 1a, 3a and 4a occurred when performing cyclic voltammetry tests. Moreover, dithienylethene 1a showed remarkable multi-color electrochromic properties during the anodic polarization. In addition, photo-mode multi-step optical storage using 2a and 3a as recording medium was performed successfully.