The morphological, bipolar charge-carrier transport, and photovoltaic characteristics of poly(3-alkylthiophene) (P3AT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blends aft studied as a function of alkyl side-chain length m, where m equals the number of alkyl carbon atoms. The P3ATs studied are poly(3-butylthiophene) (P3BT, m=4), poly(3-pentylthiophene) (P3PT, m = 5), and poly(3-hexytihiophene) (P3HT, m = 6). Solar cells with these blends deliver similar order of photo-current yield (exceeding 10 mA cm(2)) irrespective of side-chain length. Power conversion efficiencies of 3.2, 4.3, and 4.6% are within reach using solar cells with active layers of P3BT:PCBM (1:0.8), P3PT:PCBM(1:1), and P3HT:PCBM (1:1), respectively. A difference in fill factor values is found to be the main source of efficiency difference. Morphological studies reveal an increase in the degree of phase separation with increasing alkyl chain length. Moreover, while P3PT:PCBM and P3HT:PCBM films have similar hole mobility, measured by hole-only diodes, the hole mobility in P3BT:PCBM lowers by nearly a factor of four. Bipolar measurements made 6 field-effect transistor showed a decrease in the hole mobility and an increase in the electron mobility with increasing alkyl chain length. Balanced charge transport is only achieved in the P3HT:PCBM blend. This, together With better processing properties, explains the superior properties of P3HT as a solar call material. P3PT is proved to be a potentially competitive material. The optoelectronic and charge transport properties observed in the different P3AT:PCBM bulk heterojunction (BHJ) blends provide useful information for understanding the physics of BHJ films and the working principles of the corresponding solar cells.