Dual type polymer electrochromic devices (ECDs) based on potentiodynamically coated films of octanoic acid 2-thiophen-3-yl-ethyl ester (OTE), decanedioic acid bis-(2-thiophen-3-yl-ethyl) ester (DATE) and ethylene dioxythiophene (EDOT) were constructed. The former two function as anodically coloring layers and the latter as a cathodically coloring layer in between tetrabutylammonium tetrafluoroborate (TBAFB) poly(methylmethacrylate) gel media. The spectroelectrochemistry, switching ability and stability of the devices were investigated by UV–Vis spectrometry and cyclic voltammetry. These devices exhibit low switching voltages (0–1.4 V) and short switching times with reasonable switching stability under atmospheric conditions.