Size-dependent SnO2 nanocrystals (NCs)) were synthesized using a co-precipitation technique. The particle size was varied by annealing the as-prepared SnO2 NCs with the estimated size of 2.3 nm at different temperatures. The particle size obtained was 4.7, 9.0, 15.4, 19.6, and 48.0 nm at annealing temperatures of 400, 600, 800, 1000, and 1200 °C, respectively. The XRD data revealed the tetragonal rutile structured for all SnO2 NCs. The temperature-dependent photoluminescence (PL) studies showed that the sub-bridging oxygen vacancy contributed dominantly compared to the in-plane and bridging oxygen vacancies at 5K. The function of nanocrystals’ size on field emission properties is also reported. The current density was high (1.9 μA/cm2) with modest the turn-on field (8.4 V/μm) for as-prepared SnO2 QDs with the lowest size (2.3 nm) compared to the high temperature annealed SnO2 nanocrystals.