Ordered anodic aluminum oxide (AAO) templates with pores of less than 15 nm diameter and an aspect ratio (length to diameter ratio) above 3•103 have been fabricated by a non-lithographic approach; specifically, by anodizing aluminum in an ethylene glycol containing sulfuric acid electrolyte. The pores are the smallest in diameter reported for a self-ordered AAO without pore aspect-ratio limitations and good ordering, which opens-up the possibility of obtaining nanowire arrays in the quantum confinement regime interesting for efficient thermoelectric generators. The effect of the ethylene glycol addition on both the pore diameter and the ordering is evaluated and discussed. Moreover, 15 nm in diameter Bi2Te3 and poly(3-hexil thiophene) (P3HT) nanowires have been prepared using these AAO templates. As known, Bi2Te3 is currently the most efficient thermoelectric bulk material for room temperature operations and, according with theory, its Seebeck coefficient should be increased when it is confined to nanowires of diameter close to 10 nm. On the other hand, P3HT is one of the main candidates for integrating organic photovoltaic and thermoelectric devices, and its properties are also proposed to increase when it is confined to nanoscale structures, mainly due to molecular orientation effects.