Phosphate solubilizing fungi (PSF) have been widely applied to dissolve insoluble phosphates (IPs). However, the PSF usually demonstrates a different phosphate solubilizing capacity for various IPs. This study explored the mechanisms of Aspergillus niger for the dissolution of ferric phosphate (FePO4, Fe-P), and tricalcium phosphate (Ca3[PO4]2, Ca-P) regarding the tricarboxylic acid (TCA) cycle. Aspergillus niger has higher phosphorus (P) content released from Ca-P, reached the maximum value of 861 mg/L after seven days of incubation, compared with the 169 mg/L from Fe-P. Oxalic acid promoted the release of P from Ca-P through the formation of calcium oxalate. The presence of Fe-P can stimulate A. niger to secrete large amounts of citric acid, confirmed by the enhancement of citrate synthase (CS) activity. However, citric acid only promotes 0.5% of P released from Fe-P. Meanwhile, although oxalic acid still dominates the release of P from Fe-P, its abundance was significantly declined. In contrast, oxalic acid also shows a higher P release ratio in Ca-P than citric acid, i.e., 36% vs. 22%. This study points to the future usage of A. niger to dissolve IPs in soil required to enhance oxalic acid secretion.