Two new ladder-type conjugated polymers, PIDTT-DFBT-EH and PIDTT-F-PhanQ-EH, are prepared through the copolymerization of heptacyclic IDTT with F-PhanQ and DFBT electron deficient moieties. The introduction of 4-(2-ethylhexyloxy)-phenyl (EHOPh) side-chains onto the polymer is beneficial for achieving high molecular weight and good solution-processability of materials. The derived polymer solar cells yielded PCEs of 5.48% (PIDTT-DFBT-EH) and 5.14% (PIDTT-F-PhanQ-EH), without engaging post-solvent or solvent additive treatments.