Two helical conjugated ladder polymers (CLPs) have been synthesized using the photochemical cyclo-dehydrochlorination (CDHC) reaction on polychlorinated polymer derivatives. UV vis and photoluminescence spectroscopy revealed that the outer chlorinated rings (phenyl or thiophene) used for the ladderization step have a significant impact on the conformation and electronic properties of the resulting polymers. The thiophene-embedded CLP exhibits strong intermolecular interactions and excimer-like emission due to a loose coil conformation while the all-phenyl CLP exhibits a tightly packed coil conformation. The helical CLPs also show good affinity toward HiPco carbon nanotubes (CNTs) as stable dispersions were prepared.