Arrangement of polymer chains at the interface with an acceptor is one of the key issues which influences the interfacial charge transfer. Films of P3HT and P3HT:PCBM blends with the different polymer chain arrangement have been prepared from one-component and binary solvents representing a mixture of chloroform and different poor solvents with high boiling temperature. Electronic absorption and photoluminescence spectra evidenced in favor of reduced disorder of P3HT films as a result of use of poor solvents; the ordering was displayed through structuring and narrowing the spectral bands, indicative of decreasing width of Gaussian distribution of molecular transition frequencies. At the same time, transient absorption of singlet excitons showed that exciton decay in highly ordered P3HT films slows down as compared to the disordered film, and this effect was reproduced for the different poor solvents used. A more pronounced effect was revealed in P3HT:PCBM blends where much faster decay of excitons was found in disordered as-prepared P3HT:PCBM film from chloroform as compared to the annealed film or films prepared from the binary solvents. A complex behavior of polarons in the different regions of the blend film, i.e., within crystalline domains of P3HT and at the interface of P3HT/PCBM, was observed. The conclusion was drawn that chain disorder induces easier exciton dissociation and charge transfer at the P3HT/PCBM interface.