A new data treatment method for fitting spectra obtained by sulphur (S) K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to quantify the chemical S speciation at three experimental sites with arable soils receiving the same long-term field treatments. Two treatments, crop residue (CR) incorporation and farmyard manure (FYM) application, with equal applications of mineral nutrients were included in the study. In the new data treatment method, internally calibrated spectra of dilute solutions (30 mm) of model compounds were used to fit the sample spectra. This greatly enhanced the reliability of quantitative determination of contributing S species in soil samples and soil extracts. The results indicated that long-term FYM application shifted S species composition from highly oxidized towards intermediate oxidization in two of the soils, but in the third soil the opposite trend was observed. Sulphur XANES spectroscopy of acetylacetone extracts of physically protected and unprotected organic S in two of the soils revealed that physical protection was not related to S speciation; however, intermediate forms of oxidized S species appeared to accumulate in the residual S pool (not extractable by acetylacetone).