We have applied nanoporous anodic alumina films as planar optical waveguides and studied changes in the effective dielectric constants of these thin films due to various processes occurring in the pores. We demonstrate the potential of the porous anodic alumina waveguide for high sensitivity (bio-) chemical sensing with bovine serum albumin adsorption and desorption at various pH values, with subangstrom sensitivity in the effective thickness of protein adsorbed. We also monitored pore widening (alumina dissolution) with subangstrom sensitivity, which is conceptually the reverse of detecting conformal film deposition on pore surfaces. Furthermore, we monitored the exchange of pore-filling media between phosphate buffer solution and ethanol, which produces qualitatively the same response as complete pore filling with other materials by various deposition techniques. Thus porous anodic alumina films may be employed simultaneously as deposition templates and as highly sensitive detectors of processes within the pores.