Poly[3-(2-methoxyphenyl)thiophene] (PMP-Th) nanowires confined in the nano-channels of porous anodic alumina (PAA) membranes were first prepared through electrochemical deposition in cyclic voltammetry and investigated by photoluminescence (PL) spectroscopy. The morphologies and molecular structures of PMP-Th/PAA nanocomposites were studied with electron microscopy and FT-IR. The maximum absorption in UV–vis spectrum of the PMP-Th/PAA nanocomposites was located at 400–450nm. The photoluminescence spectra show that the nanocomposites have green luminescence bands with the peaks at 560–570nm. Compared to the electropolymerized PMP-Th film, the PMP-Th nanowires confined in the nano-channels of PAA membranes exhibit obvious blue-shifts in luminescent spectra and great enhancements in photoluminescence intensity. Further spectral analyses suggest that the PL enhancement could be attributed to Förster energy transfer from oxygen vacancies in PAA to PMP-Th molecules.