The physical characterization and phosphor emission spectra are presented for CaSO4 doped with Tm and Cu. All spectral wavelengths are related to electronic transitions of Tm3+ ions. The powder X-ray diffraction pattern showed that the compound exhibits orthorhombic structure and all reflections were indexed without any other secondary impurity phases. Chemical and structural properties of the samples have been characterized by means of Raman spectroscopy and environmental scanning electron microscope (ESEM) with an attached X-ray energy dispersive system (EDS). Group frequencies concept is essential point to the interpretation of the bands due to the main SO4 vibrational units and these displayed main characteristic intensive Raman bands including typical strong intensity at 1016 cm(-1) that corresponds to v(1)SO(4) vibrational mode. From the spatially-resolved cathodoluminescence (CL) spectrum, main emission bands of Tm3+ centered at 346, 362, and 452 nm, due to the respective transitions of P-3(0) -> H-3(4), D-1(2) -> H-3(6), D-1(2) -> F-3(4) were clearly identified. The study is novel as no such CL-ESEM data are available for this doped compound. (C) 2015 Elsevier B.V. All rights reserved.