Divalent metal complexes (MTpyV) of terpyridine modified asymmetric viologen (TpyV) with Fe(II), Co(II), Ru(II), and Ni(II) were prepared. Single-layered electrochromic devices (ECDs) were constructed by sandwiching the ion gel containing MTpyV. MTpyVs showed a fast transition from a dicationic state to a radical ion state, whereas the bleaching was delayed for a long time, unlike the conventional viologen-based ECDs. From the cyclic voltammetry and the spectroelectrochemical studies, the facile oxidation processes of M(II) to M(III) and Tpy−• to Tpy0 were noticed, implying that the transition from the colored radical cation (V+•) to dicationic species (V2+) was significantly retarded. Consequently, the color appearance of MTpyV ECDs was maintained for a long time after removing the applied potential. This behavior was heavily dependent on the chelated metals. Owing to the better redox behaviors of Ni(II) and Ru(II), NiTpyV and RuTpyV showed an optical memory effect for extended time compared to Fe(II) and Co(II) complexes. Especially, NiTpyV exhibited a remarkable optical memory effect, accompanied by an intense colorless-to-blue transition. The switching behavior of NiTpyV is worthwhile to notice since it offered a highly transmissive color at a dicationic state without showing MLCT absorption in the visible region. Current results suggest the effective protocol in a material design suitable for the optical memory electrochromic devices based on viologen derivatives.