Abstract The nature of secondary geochemical dispersion of As, Sb, Hg and Bi in soil and ground water of the semi-arid, tropical, Archaean, auriferous, Hutti-Maski greenstone belt has been investigated for identification of appropriate geochemical techniques for Au exploration in similar terrains. Results indicate that the <180 μm size-fraction of C-horizon soil is an appropriate sampling medium for delineating pedogeochemical anomalies of As, Sb, Hg and Bi related to gold mineralisation. These pedogeochemical anomalies along with anomalous values of alkalinity, chloride, sulphate, As and Sb in groundwater are controlled significantly by primary mineralisation located along shear zones in the greenstone belt. Arsenic anomalies in soil are broad, whereas, those of Sb and Bi are restricted to narrow zones directly over mineralised areas. In contrast, Hg anomalies around known mineralised areas are irregular and do not clearly demarcate the mineralised areas. The study indicates that anomalies of As, Sb and Hg in soil are principally hydromorphic, whereas those of Bi are clastic. The study recommends use of groundwater sampling at 2–3 km spacing with routine analysis of chloride, sulphate and alkalinity along with As and Sb in the first phase. This may be followed up with sampling of C-horizon of soils on a 1 km square grid for As-anomalies. Arsenic-anomalous areas may be sampled for As, Sb, Hg and Bi on a 500 m square grid for detailed exploration.