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Abstract: A series of double-perovskite Sr2CaW x Mo1−x O6 (x=0−1) matrices were prepared by solid state reactions. The phase and the optical properties of the samples were investigated by X-ray diffraction (XRD), photoluminescence (PL) and luminescence decay. The results of XRD indicate that the structure of matrix is orthorhombic double-perovskite with space group P21/n. The hosts show intense blue emission at around 435 and 468nm upon the excitation of near-ultraviolet 290nm due to W–O charge transfer band (CTB), and weak emission at around 560nm upon the excitation of 360nm due to Mo–O CTB. The luminescence decay of the hosts was investigated as well. [Copyright &y& Elsevier]