New semiconducting soluble poly(arylene sulfide)s were synthesized by Wittig polycondensation. The arylene moieties consist of distyrylbiphenyl (P1) and distyrylbithiophene (P2) pi-conjugated systems. The polymers are fully amorphous and show good thermal stability. The absorption and photoluminescence properties of the polymers were investigated. P1 film has an optical gap of 2.95eV and exhibits green-blue fluorescence. P2 shows a longer effective conjugation length with a gap of 2.42eV and emits in the orange region. The HOMO/LUMO energy levels were estimated by cyclic voltammetry measurements. Single-layer diodes were fabricated and show relatively low turn-on voltages.