Highly ordered and dense TiO2 nanopore arrays are directly nanoimprinted on a transparent conductive glass substrate by using a polymethylmethacrylate/polydimethylsiloxane (PMMA/PDMS) composite soft template, which is replicated from an anodic aluminum oxide (AAO) replica mold. Results indicate that heat infiltration under vacuum conditions can ensure complete filling of PMMA into the AAO pores, and that free-standing PMMA nanorods with an aspect ratio more than 5 can be obtained by adjusting the AAO pore depth based on a freeze-drying technique. TiO2 nanopore arrays with different diameters from 30 to 300 nm and inter-pore distances between 70 and 450 nm can be easily fabricated by using the corresponding templates with different sizes. Preliminary solar cells are also assembled with a heterojunction of conjugated polymer/TiO2 nanopore arrays. Results indicate that the construction of poly-(3-hexylthiophene) (P3HT)/TiO2 nanopore arrays can be more helpful in quenching the PL emission of P3HT than that of P3HT/flat TiO2 film, and a maximum efficiency of about 0.32% can be obtained for a photovoltaic device with a TiO2/[6,6]-phenyl-C-61-butyric acid methyl ester (PCBM)/P3HT structure. (C) 2011 Elsevier B.V. All rights reserved.