In this study, the photoluminescence properties of Y3Al3MgSiO12:Cr3+ (YMASG:Cr3+) and Y3Al3MgSiO12: 2%Ce3+, Cr3+ (YMASG:2%Ce3+, Cr3+) were investigated, and the energy transfer from Ce3+ to Cr3+ were examined. All phosphor samples were prepared by the aqueous sol–gel method. The phase purity and surface morphology of the obtained sample was evaluated using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). To determine the photoluminescence (PL) properties of YMASG:Cr3+ and YMASG:2%Ce3+, Cr3+, emission and excitation spectra along with reflection spectra were recorded. PL decay measurements were also performed, and PL lifetime values were determined. It was found that Ce3+ → Cr3+ energy transfer efficiency increases with increasing Cr3+ concentration. To investigate the temperature-dependent emission of YMASG:Cr3+ and YMASG:2%Ce3+, Cr3+, PL emission, and PL decay measurements were conducted in a temperature range from 77 to 500 K. Temperature-dependent PL decay measurements also revealed that the Cr3+ ions mainly cause thermal quenching of YMASG:2%Cfe3+, 1%Cr3+ emission. To check the suitability of synthesized materials to be applied for greenhouse illumination, two pcLEDs containing YMASG:Cr3+ and YMASG:Ce3+, Cr3+ phosphors were constructed. PcLED prototypes applicability for efficient horticulture lighting was also investigated within this study.