A metal-clad waveguide (MCWG) sensor comprised of a nanoporous waveguiding layer on a metal cladding layer is advantageous in sensing of biomolecules because of a high surface area of nanopores and a sharp dip in the reflection spectrum due to characteristics of the MCWG mode. Here, a porous anodic alumina (PAA)/aluminum (Al) film was fabricated on a glass substrate as a MCWG sensor with the Kretschmann geometry, and the sensor response was examined for both colorless bovine serum albumin (BSA) and colored metal complexes by measurements of reflection spectra and Fresnel calculations. The BSA adsorption on the PAA layer induced a parallel redshift of the waveguide coupling dip in the reflection spectrum. The experimental results were well simulated by the five-phase Fresnel calculations which indicated that the redshift of the dip was linearly dependent on the adsorbed amount of BSA. When the response of a MCWG sensor with a PAA layer was compared with that of a MCWG sensor with a nonporous alumina layer, the former showed larger redshift than the latter, due to a large adsorbed amount of BSA in the PAA layer with high surface area. For the adsorption of colored Ru[Bphen(3)](2+) and Fe[Phen(3)](2+), the effect of both the real and imaginary parts of the complex refractive index on the sensor response was examined. As a result, a redshift of the waveguide coupling dip was observed for both metal complexes irrespective of the wavelength region examined; this could be ascribed to the changes in the real part of the refractive index due to the adsorption of metal complexes on the PAA layer. Meanwhile, an increase in the reflectivity was observed when the coupling wavelength was close to that of the absorption bands of the metal complexes; this could be ascribed to the changes in the imaginary part of the refractive index of the PAA layer. Using the sensor response caused by the changes in the imaginary part, absorption spectral profiles of metal complexes could be reproduced.