Coherent anti-Stokes Raman scattering (CARS) microscopy is a powerful imaging technique that can provide chemical information of organic and nonorganic materials through vibrational spectroscopy. However, its contrast is not sufficient for monitoring thin film materials. In this study, silica microspheres were employed for enhancing the signal contrast in CARS imaging. One layer of optically transparent silica microspheres was self-assembled onto polymer grating samples to enhance the CARS signals. The highest contrast enhancement factor of 12.5 was achieved using 6.1-μm-diameter microspheres. Finite-difference time-domain method (FDTD) simulation was conducted to simulate the contrast enhancement with silica microspheres of different diameters.