Hybrid thin film nanostructures composed of metal nanoparticles (NPs) and self-assembled polymer films with different spatial distributions of NPs were analyzed by optical waveguide spectroscopy (OWS). Specifically, the dielectric constants were calculated using effective medium theory for the incorporation of 1 vol% Au NP into the block copolymer (BCP) films having a cylindrical nanodomain morphology. Three cases were considered: uniform distribution of NPs in the film; selective distribution of NPs only in the cylindrical domains; and segregation of NPs to the center of the cylindrical domains. The optical waveguide spectra derived from the calculated dielectric constants demonstrate the feasibility of experimentally distinguishing the composite nanostructures with different inner morphologies in the hybrid metal NP-BCP nanostructures, by the measurement of the dielectric constants using OWS.