Soluble lead (Pb) can be immobilized in pure systems as pyromorphite by adding sources of phosphorus (P), but uncertainties still remain in natural systems. Knowledge of PZC is important to predict the ionization of functional groups and their interaction with metal species in solution. This study utilized the Pb- and As-contaminated soils to determine the combined effect of pH with respect to PZC and different rates of P-application on pyromorphite formation, and Pb and arsenic (As) bioaccessibility as impacted by speciation changes. Solution chemistry analysis along with synchrotron-based Pb- and As-speciation, and bioaccessibility treatment effect ratios (TERs) were conducted. Results indicated no significant effect of PZC on pyromorphite formation in P-amended soils; however, the TERPb appeared significantly lower at pH>pHPZC and higher at pH<pHPZC (α = 0.05). In contrast, the TERAs was significantly higher at pH>pHPZC, compared to the other two treatments, for the tested soils. The lack of conversion of soil Pb to pyromorphite may be attributed to presence of stable minerals limiting soluble-Pb availability and high organic matter content of the tested soils.