A polarization-maintaining (PM) fiber Mach-Zehnder (MZ) interferometer has been established to measure the EO effect of very thin film materials with optical anisotropy. Unlike a common MZ interferometer, all the components are connected via polarization-maintaining fibers. At the same time, a polarized DFB laser with a maximum power output of 10mW is adopted as the light source to induce a large extinction ratio. Here,we take it to determine the electro-optical coefficients of a very thin superlattice structure with GaAs, KTP, and GaN as comparative samples. The measured EO coefficients show good comparability with the others.