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The effect of thickness ratio of two materials on the residual stress was studied in HfO2/SiO2 multilayers deposited by electron beam evaporation on BK7 glass substrates. An optical interferometer was used to analyze the residual stress, and X-ray diffraction (XRD) was applied to characterize the structural properties. The results showed that the residual stress of multilayers was compressive when the optical thickness ratio of HfO2 to SiO2 was 1:3. Then the value of residual stress decreased with the increase of optical thickness ratio, the residual stress became tensile when the thickness ratio increased to 3:1. HfO2 was monoclinic and SiO2 was amorphous in all the multilayers. The microstructures of 1:3, 6:13 and 1:1 multilayers were similar. For crystal plane m(020), the interplanar distance decreased and the crystallite size increased when the optical thickness ratio increased to 3:1. In addition, the evolutions of residual stress were corresponding with the variations of microstructure to some extent.