Red color-emitting CaGd2ZnO5:Eu(3+) (CGZO:Eu(3+)) nanophosphors were synthesized by a facile sol-gel process. The structural and luminescent properties of these phosphors were investigated as a function of annealing temperature and Eu(3+) ion concentration. The orthorhombic phase was confirmed at different annealing temperatures, showing an irregular morphology within the nanoscale range. Photoluminescence (PL) excitation spectra of CGZO:Eu(3+) showed host absorption band (HAB), charge transfer band (CTB), and intense f-f transitions of Eu(3+) in the violet and blue wavelength regions. The CTB intensity increased and the HAB intensity decreased with increasing annealing temperature or Eu(3+) ion concentration. The CGZO:Eu(3+) exhibited a strong absorption in the blue region as compared to the CTB and had a superior property compared to available commercial phosphors. This feature facilitates the fabrication of high color rendering index white light-emitting diodes for display systems. In PL spectra, an intense red emission was observed due to the hypersensitive (5)D0→(7)F2 transition with good asymmetry ratio and chromaticity coordinates. Optimized annealing temperature and concentration of Eu(3+) ions were observed for CGZO host lattice based on the 466 nm excitation wavelength. The cathodoluminescent properties were also similar to the PL results.