We report the construction and testing of a chirped diffraction grating, which serves as a substrate for surface plasmon-enhanced optical transmission. This grating possesses a spatial variation in both pitch and amplitude along its surface. It was created by plasma oxidation of a curved poly(dimethoxysilane) sheet, which resulted in nonuniform buckling along the polymer surface. A gold-coated replica of this surface elicited an optical response that consisted of a series of narrow, enhanced transmission peaks spread over the visible spectrum. The location and magnitude of these transmission peaks varied along the surface of the grating and coincided with conditions where surface plasmons were excited in the gold film via coupling to one or more of the grating’s diffracted orders. A series of measurements were carried out using optical diffraction, atomic force microscopy, and normal incidence optical transmission to compare the grating topology to the corresponding optical response. In addition, the impact of a thin dielectric coating on the transmission response was determined by depositing a thin silicon oxide film over the grating surface. After coating, wavelength shifts were observed in the transmission peaks, with the magnitude of the shifts being a function of the film thickness, the local grating structure, and the diffracted order associated with each peak. These results illustrate the ability of this surface to serve as an information-rich optical sensor whose properties can be tuned by control of the local grating topology.