Free-standing nanorod arrays of a thermally cross-linked semiconducting triphenylamine were fabricated on conductive ITO/glass substrates via an anodic aluminum oxide (AAO) template-assisted approach. By using a solution wetting method combined with a subsequent thermal imprinting step to fill the nanoporous structure of the template with a cross-linkable triphenylamine derivative, a polymeric replication of the AAO was obtained after thermal curing and selective removal of the template. To obtain well-aligned and free-standing nanorod arrays, aggregation and collapse of the nanorods were prevented by optimizing their aspect ratio and applying a freeze-drying technique to remove the aqueous medium after the etching step. Because of their electrochemical properties and their resistance against organic solvents after curing, these high density nanorod arrays have potential application in organic photovoltaics.