The use of thin film block copolymers (BCP) with controlled microdomain orientation as planar optical waveguides was described. The thin films of block copolymers were investigated for their optical waveguiding properties by optical waveguide spectroscopy (OWS) . It was found that resonance coupling between surface plasmons and incident photons can occur at a metal/dielectric interface. The thin films of BCPs with cylindrical microdomains oriented normal to the substrate surface were successfully coupled in the Kretschmann configuration. The porous BCP templates, which were shown to be stable in the PBS solution and ethanol, also showed promise for use as a versatile model platform, by which interactions with biological substances can also be probed.