Ten tripod-shaped electrochromic materials (compound 1–10) were designed and synthesized by esterification of 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid with different alcohols and phenols. These materials have a 2,4,6-triphenyl-1,3,5-triazine core and three ester side arms, forming an electron donor–π-acceptor structure. The electrochemical and optical properties of 1–10 were characterized by cyclic voltammetry and ultraviolet–visible spectroelectrochemistry. The conjugated structure of 1–10 markedly influenced their electrochemical properties. Electrochromic devices containing some of these compounds (1, 2, 4, 5, and 10) displayed intense color changes, fast switching times (<2 s), high optical contrast (>60%), good switching stability, high optical density (>1.0), and high coloring efficiency (>1000 cm² C⁻¹). The colored state of these devices strongly depended on the conjugated structure of the tripod-shaped component. Short chain lengths (compounds 1 and 2) and electron-donating groups (compounds 4, 5, 8, and 10) were beneficial to electrochromic properties, whereas a longer chain length (compound 3) and electron-withdrawing groups (compounds 6 and 9) adversely affected electrochromic properties.