Three electron-deficient conjugated polymers based on perylene diimide (PDI) units, namely, poly[(N,N'-didodecyl-3,4,9,10-perylene diimide-1,7-diyl)-alt-(9,9-dihexylfluorene-2,7-diyl)] (PPDIF), poly{(N,N'-didodecyl-3,4,9,10-perylene diimide-1,7-diyl)-alt-[N-(2-ethylhexyl) carbazole-3, 6-diyl]} (PPDIC) and poly{(N,N'-didodecyl-3,4,9,10-perylene diimide-1,7-diyl)-co-[N-(2-ethylhexyl) carbazole-3,6-diyl]-co-(9,9-dihexylfluorene-2,7-diyl)} (PPDICF) have been synthesized via Suzuki coupling reaction, and their chemical structures are confirmed by (1)H NMR, (13)C NMR and FT-IR. All these polymers show broad absorption bands in 250-700 nm, and their optical band gaps are calculated to be similar to 1.7 eV. Cyclic voltammetry results confirm that the objective macromolecules possess high electron affinity of similar to 3.9 eV. By employing poly-3-hexylthiophene (P3HT) as electron donor and PPDIC as electron acceptor, all polymer solar cells (aPSCs) with bulky heterojunction structure have been fabricated, preliminary results indicate they have one of the most highest open-circuit voltage (V (oc)) (0.86 V) reported so far in aPSCs with PDI-based polymers as electron acceptor.