In this study, thermally stable and solution-processable conjugated poly[N-(2-ethylhexyl)-3,6-carbazole-alt-aniline] copolymer containing alternating carbazole and triarylamine moieties in the polymer backbone was synthesized in a good yield by Pd-catalyzed polycondensation. The polymer exhibited maximum UV-vis absorption peak at 309 nm and maximum photoluminescence peak at 452 nm. From the optical and electrochemical characterization, the band gap, HOMO, and LUMO energy levels of the polymer were measured to be 2.91 eV, -5.19 eV, and -2.28 eV, respectively. The polymer was used to examine the hole-transporting performance to a solid-state dye-sensitized solar cell (ssDSSC). The ssDSSC fabricated with poly[N-(2-ethylhexyl)-3,6-carbazole-alt-aniline] copolymer showed a PCE of 1.50% with J(sc) = 3.76 mA/cm(2), V-oc = 538 mV, and FF = 74.3%, implying the potential of the synthesized polymer as a hole-transport material (HTM) to ssDSSC.