The red and NIR emissions and exchange interactions observed due to Cr3+ ion when present in an oxygen environment makes it an interesting candidate for magnetic studies and optoelectronic applications. In this work, we observed a near-white light emission (near-WLE) and the selective tuning to the near-infrared (NIR) luminescence in Ga substituted lanthanum chromite (Ga:LaCrO3) perovskite with electron-beam excitation. The near-WLE observed in Cathodoluminescence (CL) study, arises from the combination of 4T1(F) →4A2 (blue), 4T1(P) →4A2 (green) and 4T2→4A2 (red) spin allowed transitions and 2E→4A2 spin forbidden transitions from Cr3+. The spin allowed transitions from Cr3+ are not common, however can result by adjusting the Cr3+/Ga3+ concentration in the host lattice. The NIR emission originates from the selective 2E→4A2 transition, which dominates with the increasing concentration of Ga3+ ions. The Density Functional Theory (DFT) calculations point out the presence of extra electronic states with Ga substitution, which validates the observation of NIR emission in Ga substituted samples. Sharp lines were observed in the NIR emission spectrum for the LaCr0.5Ga0.5O3 sample on excitation with 488 nm laser. Further investigations reveal the presence of lasing due to the pair emission of Cr3+ ions in the system. The microcrystals present in the system work as suitable cavities for the lasing in the NIR region. The time-resolved Photoluminescence (TRPL) spectrum of the sample has illustrated a sub-nanosecond lifetime and indicates 99% of the lifetime is contributed from the pair emission. The short lifetime can be attributed to a high concentration of Cr3+ ions, which enhances the Cr3+-Cr3+ exchange interaction and pair emission, and is evidenced by electron spin resonance study. For exploring the exchange interaction between Cr3+ ions, magnetic studies have been carried out. The pristine LaCrO3 is an antiferromagnetic material with transition temperature near 290 K. The inclusion of Ga at the Cr site will cause a magnetic dilution in the system and will reduce the strong antiferromagnetic coupling. A hyperfine interaction is observed in the LaCrO3 system at low temperature in both ESR and heat capacity measurements. This strong hyperfine interaction in LaCrO3 is due to the presence of strong antiferromagnetic interaction present in the system and which disappears with magnetic dilution on Ga substitution.