We successfully address the challenge of aligning single-walled carbon nanotubes (SWNTs) and conjugated polymer chains in composite nanofibers for enhancing their opto-electrical properties. A pore-filling template strategy has been developed to prepare such nanocomposites from SWNTs and poly(para-phenylene vinylene) (PPV) chains, with both species well-oriented aligned along the pore axis. Addition of the SWNTs leads to a remarkable increase in photocurrent of four orders of magnitude as compared to equivalent pristine PPV nanofibers. Further analysis indicates that the strong photocurrent enhancement is not simply an effect of alignment, but additionally benefits from alignment-enhanced interaction of polymer chains with SWNTs, as supported by density functional theory (DFT) calculations.