The change of point of zero charge (PZC) with soil development degree and its implications for pedogenesis in tropical areas were discussed in this research. A soil chronosequence consisting of six soil profiles with age ranging from 0.09 Ma to 2.30 Ma, developed on basalt in the tropical Hainan Island, were collected. The means of potentiometric titration in different electrolyte strengths was used to measure the soil PZC, and the mineralogical composition was determined by X-ray diffraction analysis (XRD). The results showed that the soil PZC increased with increasing basalt age and degree of soil development, which may be due to the change of clay minerals and the enrichment of iron oxides. The potentiometric titration curves indicated that the permanent negative soil charge was reducing during soil development, combined with the decline of soil fertility retention ability. Compared with some other indices, the soil PZC could be a better indicator to evaluate the soil development time and soil weathered degree.