This paper presents a nondestructive ultrasound testing method for characterization of the resonant frequencies of polydimethylsiloxane (PDMS) thin film by using a miniature fiber optic photoacoustic (PA) probe. The PA probe was fabricated with an optical fiber and a synthesized gold nanocomposite. During the experiment, a cured PDMS thin film with a thickness of 220 μm was immersed into a water medium using a custom-designed holder to clamp the film. An acoustic pulse was generated by the PA probe and propagated through the water media to excite the fixed film. A fiber optic pressure sensor based on the Fabry-Perot principle was used to collect the excited acoustic signals on the other side of the film. The acquired response of the acoustic pulse was used to compute the resonant frequencies of the PDMS thin film based on a deconvolution method.