The process of organic materials increasing soil pH has not yet been fully understood. This study examined the role of cations and organic anions in regulating soil pH using organic compounds. Calcareous soil, acid soil, and paddy soil were incubated with different simple organic compounds. pH was determined periodically and CO2 emission was also measured. Mixing organic acids with the soil caused an instant decrease of soil pH. The magnitude of pH decrease depended on the initial soil acidity and dissociation degree of the acids. Decomposition of organic acids could only recover the soil pH to about its original level. Mixing organic salts with soil caused an instant increase of soil pH. Decomposition of organic salts of sodium resulted in a steady increase of soil pH, with final soil pH being about 2.7-3.2pH units over the control. Organic salts with the same anions (citrate) but different cations led to different magnitudes of pH increase, while those having the same cations but different anions led to very similar pH increases. Organic salts of sodium and sodium carbonate caused very similar pH increases of soil when they were added to the acid soil at equimolar concentrations of Na+. The results suggested that cations played a central role in regulating soil pH. Decarboxylation might only consume a limited number of protons. Conversion of organic salts into inorganic salts (carbonate) was possibly responsible for pH increase during their decomposition, suggesting that only those plant residues containing high excess base cations could actually increase soil pH.