We have investigated novel beam splitter (BS) materials to relax thermal issues under irradiation of a high-average-power visible and near infrared (VIS–NIR) laser beam. The material should efficiently reflect a high-order harmonic beam in the extreme ultraviolet (XUV) spectral region and transmit a VIS–NIR fundamental laser beam at a Brewster incidence for the latter beam. We have investigated optical and thermo-mechanical properties of crystalline silicon carbide (SiC), diamond, and rutile since they exhibit high transparency and high index of refraction for a VIS–NIR light. We also address thermal issues of conventional opaque BS materials by measuring their thermal distortion. We have shown that crystalline SiC is the most promising candidate among the other materials because of a high reflectivity for XUV light, as well as an ignorable thermal distortion. The surface flatness of a crystalline SiC plate must be improved to realize an applicable BS in the XUV spectral region.