X-ray excited optical luminescence (XEOL) spectroscopy allows the establishment of the links between the optical properties and the structure and chemical composition of a wide range of materials and devices. Additionally, XEOL is often used to understand the mechanism of radiative recombination and to measure X-ray absorption fine structure (XAFS) via the resulting photoluminescence yield. In this talk, we will present the new setup to perform steady-state XEOL and simultaneous XEOL and XAFS characterizations at beamline P65. A state-of-the-art optical detection system covers a wide spectral range of 300 - 1700 nm and a customer designed He-flow cryostat allows a controlled sample temperature within the range of 5 - 300 K. The setup functionality will be illustrated by typical case studies, including the low temperature XEOL on polycrystalline CuInSe2 thin film, single crystalline GaN thin film and single crystalline ZnO bulk semiconductors.