Er3+-activated CdMoO4 phosphors were prepared by a traditional high-temperature solid-state method. The crystal structure, photoluminescence (PL) characteristics and performance in non-contact thermometry of as-prepared phosphors were studied in detail. Benefiting from the 3D network structure of CdMoO4 host, the desirable green emission of Er3+-based phosphors were observed. Especially, based on the thermally coupled energy levels, the obtained phosphors show enhanced emission intensity in high temperatures. When applied to the temperature sensor based on the fluorescence intensity ratio (FIR), the prepared CdMoO4:0.02Er3+ phosphor show an excellent sensitivity (0.875% K−1) at 483 K. Therefore, it is demonstrated that the as-prepared Er3+-activated CdMoO4 phosphors have a promising potential application in both solid-state lighting and non-contact thermometry.