This work presents a simple method to generate ordered conjugated polymer nanoarrays through a pore-filling process for nanoporous polymer templates so as to enhance the efficiency of photoluminescence (PL). PL results combined with the morphological evolution examined by scanning probe microscopy revealed that the enhanced PL reaches maximum intensity as the template pores are completely filled by conjugated polymers. Polarized PL spectroscopy and grazing incidence Fourier transform infrared spectroscopy were used to determine the chain orientation of templated conjugated polymer; the spectroscopic results indicate a parallel chain orientation along the cylindrical direction of nanopores. The induced alignment of the polymer chains is attributed to a nanoscale spatial effect that increases the PL intensity and the lifetime of the conjugated polymer. The enhanced luminescence of nanostructured conjugated polymers is highly promising for use in designing luminescent nanodevices.