In this study, six conjugated oligomers containing D–A structures were synthesized using the Stille coupling reaction and named PHZ1–PHZ6. All the oligomers utilized demonstrated excellent solubilities in common solvents and notable color variations in the domain of electrochromic characteristics. By designing and synthesizing two electron-donating groups modified with alkyl side chains and a common aromatic electron-donating group, as well as cross-binding them with two electron-withdrawing groups with lower molecular weights, the six oligomers presented good color-rendering efficiencies, among which PHZ4 presented the best color-rendering efficiency (283 cm2·C−1). The products also demonstrated excellent electrochemical switching-response times. PHZ5 presented the fastest coloring time (0.7 s), PHZ3 and PHZ6 presented the fastest bleaching times (2.1 s). Following 400 s of cycling activity, all the oligomers under study showed good working stabilities. Moreover, three kinds of photodetectors based on conducting oligomers were prepared, and the experimental results show that the three photodetectors have better specific detection performances and gains. These characteristics indicate that oligomers containing D–A structures are suitable for use as electrochromic and photodetector materials in the research.