By use of Photocatalytically Initiated Electroless Deposition (PIED) we have deposited macroporous metal films with highly ordered arrays of sub-µm (hemi)spherical pores directly onto the surface of insulating substrates for the first time. This has been achieved by sensitisation of the target substrate with TiO2 photocatalyst followed by PIED of the target metal into the interstitial spaces of a template comprised of hexagonally close packed polystyrene microspheres.