Chitosan microcapsules draw attention due to their biodegradability, biocompatibility, antibacterial behavior, low cost, easy processing, and the capability to be used for different applications. This study utilized the electrospraying technique for the chitosan microcapsules formulation. As a novel cross-linking agent, a mixture of oxalic acid and sodium phosphate dibasic was utilized as a collecting solution for the first time in the electrospraying of chitosan microcapsules. Scanning Electron Microscopy (SEM) was utilized to optimize the spherical morphology and size of the experimentally obtained microcapsules. The different parameters, including chitosan concentration, applied voltage, flow rate, and tip-to-collector (TTC) distance, affecting the microcapsules’ size, sphericity, yield, and combined effects were optimized using Surface Responses Methodology (RSM). The Analysis of Variance (ANOVA) was utilized to obtain the impact of each parameter on the process responses. Accordingly, the results illustrated the significant impact of the voltage parameter, with the highest F-values and least p-values, on the capsule size, sphericity, and yield. The predicted optimum conditions were determined as 5 wt% chitosan concentration, 7 mL/h flow rate, 22 kV, and 8 cm TTC distance. The predicted responses at the optimized conditions are 389 µm, 0.72, and 80.6% for the capsule size, sphericity, and yield, respectively. While the validation of the model prediction was conducted experimentally, the obtained results were 369.2 ± 23.5 µm, 0.75 ± 0.04, and 87.3 ± 11.4%, respectively. The optimization process was successfully examined for the chitosan microcapsules manufacturing.