A novel ruthenium-free organic dye, 3-(5-(4-(di-p-tolylamino)styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-cyanoacrylic acid (coded as H01), is synthesized in a short sequence. The dye is composed of a di(p-tolyl)phenylamino moiety as an electron donor, a cyanoacrylate moiety as an electron acceptor, and an ethylenedioxythiophene unit as the spacer to bridge the donor and the acceptor. The as-prepared H01 dye is employed as a sensitizer in a dye-sensitized nanocrystalline TiO2 solar cell, and the short-circuit photocurrent density (Jsc), open-circuit voltage (Voc), and fill factor (ff) of the device under AM 1.5 (100 mW cm−2) irradiation, are 15.22 mA cm−2, 0.67 V, and 0.72, respectively, corresponding to an overall conversion efficiency (Eff) of 7.33%.