The most critical aspect in the assembly of phosphor-converted white light-emitting diodes (pc-WLED5) is how to stabilize the device in a practical environment. The high applied currents can generate enormous heat up to more than 100 degrees C, and such a continuous illumination process will lead to serious effects concerning the stability of the device. Therefore, the new search for examples to fully suppress thermal quenching effect is a real challenge. In this study, a novel Eu3+-activated CaMgGeO4 (CMGO) phosphor of olivine type is developed via a conventional solid-state reaction. The results reveal that Eu3+ occupies the low symmetric Ca2+- site of this host. Upon visible-light sensitization at 464 nm, a dominant red emission band with maximum at 612 nm is witnessed. Its full width at half-maximum (fwhm) is merely similar to 4.37 nm, and a high color purity of around 94% is achieved. Their corresponding Commission Internationale de L'Eclairage (CIE) coordinates are very close to standard red color coordinates (0.666, 0.333). The influence of concentration and temperature on the optical property has been explored. It has been discovered that the optimized sample (CMG0:0.01Eu(3+)) is not influenced by the thermal quenching effect and its fluorescent intensity is improved even up to 473 K, which is mainly attributed to the incorporation of abundant trap sites generated by the nonequivalent substitution Eu3+ for Ca2+. After it is integrated into commercially available YAG:Ce3+ phosphor-based pc-WLEDs, the excellent optical parameters of the fabricated WLEDs are evaluated. The correlated color temperature (CCT) varies from cool white (6458 K) to warm (4370 K), and the color rendering index (CRI) increases from 78 to 86 under a high flux operating current of 200 mA. Furthermore, the chromaticity coordinates remain almost stable with the increasing drive current from 200 mA to 1000 mA. It is highly expected that CaMgGeO4:0.01Eu(3+) will become a suitable red phosphor for the preparation of white LEDs with high efficiency.