Sweet potato starch wastewater (SPSW) is an industrial food-processing waste product, which is a significant pollution source due to its high chemical oxygen demand (COD), nitrogen, and phosphorus loads. The influence of hydrolytic acidification (HA) process on C, N, and P as well as other main parameters were evaluated. It is essential to treat these wastewaters with effective methods such as HA, a general pretreatment application. In this study, we investigate the scientific link between the changes of different fractions of C, N, and P with particle size distribution in response to the newly introduced HA process. Results showed that the levels of COD, TN, and TP remained ultimately stable; pH and suspended solids (SSs) decreased obviously. HA process exhibits excellent capability of reducing the larger particulars (with diameter of >5 μm) into smaller ones (with diameter of <0.1 μm). The most significant initial concentration contribution to COD, TN, and TP pollution came from particles and matter with a diameter of >5 μm, at 41.8, 57.3, and 43.5%, respectively. While the most significant contribution to COD, TN, and TP was resulting from micro-molecular size particles (<0.1 μm) after 48 h. The smallest particles (<0.1 μm) were the most dominant contribution to all pollutants measured, with COD, TN, and TP contributions of 63.2, 50.4, and 59.3%, respectively. While the contribution of larger particles (particle size >5 μm) reduced to 10.2, 15.3, and 7.1%, respectively.