In the processing of colliding atomizers, a small change in the inclination of each orifice will double the impact angle, seriously affecting its atomization performance. In this paper, the influence of slight impact angle deviation on atomization performance was studied in steps of 1°, quantitatively, for the first time. The cavitation effect of the flow field was combined with the shape and parameters of the atomization field. FLUENT was used to simulate the internal flow field, and an independently designed atomizer with transparent nozzles was used to detect the internal flow field in real time. The collision atomization experimental platform and the laser interference particle measurement platform were built independently, and the collision angle was adjusted through a high-precision rotating table to establish the relationship between collision-angle deviation (60° ± 5°) and the atomization field performance (Sauter mean diameter, atomization cone angle, and spatial distribution of droplets). The experimental results showed that under the same injection pressure, the increase in the collision angle led to an decrease in the Sauter mean diameter and an increase in the atomization cone angle. Taking 60° as the benchmark, the particle size distribution was concentrated at ~150 μm to 300 μm within the variation range of ±2°, and the peak positions were very similar.