Sensitization and mineralization synergistically effects of V to Cr-doping ZrSiO4 based jewel green pigment were studied in this work. The sensitization and mineralization effects of pigment were characterized via several analysis techniques, such as XRD, SEM, EDS, TEM, XPS, UV–Vis–NIR spectrophotometer and CIE L*a*b*. Experimental results show that V can serve as a mineralizer to promote the formation of zircon phase and can also serve as a sensitizer to promote the coloration of Cr. The energy can be transferred from 2E level of V4+ to nearby Cr3+, promoting the 4T1 (4F) energy level transition of Cr3+. There is no loss of silicon and zirconium throughout the process, and the pigment presents a series of pure green gradient by changing the amount of V. When the amount of V addition is 0.08, a single zircon phase shows in the pigment with a jewel green color (L* = 56.89, a* = -16.36, b* = -4.42), and the test results show that the pigment possesses a good near-infrared reflection effect. The prepared pigment has some promising application values.