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This study presents multiple sulphur isotope (32S, 33S, 34S, 36S) data on pyrites from silicified volcano‐sedimentary rocks of the Paleoarchean Onverwacht Group of the Barberton greenstone belt, South Africa. These rocks include seafloor cherts and felsic conglomerates that were deposited in shallow marine environments preserving a record of atmospheric and biogeochemical conditions on the early Earth. A strong variation in mass independent sulphur isotope fractionation (MIF‐S) anomalies is found in the cherts, with Δ33S ranging between −0.26‰ and 3.42‰. We explore possible depositional and preservational factors that could explain some of this variation seen in MIF‐S. Evidence for microbial activity is recorded by the c. 3.45 Ga Hooggenoeg Formation Chert (HC4) preserving a contribution of microbial sulphate reduction (−Δ33S and –δ34S), and a c. 3.33 Ga Kromberg Formation Chert (KC5) recording a possible contribution of microbial elemental sulphur disproportionation (+Δ33S and –δ34S). Pyrites from a rhyo‐dacitic conglomerate of the Noisy Formation do not plot along a previously proposed global Felsic Volcanic Array, and this excludes short‐lived pulses of intense felsic volcanic gas emissions as the dominant control on Archean MIF‐S. Rather, we suggest that the MIF‐S signals measured reflect dilution during marine deposition, early diagenetic modification, and mixing with volcanic/hydrothermal S sources. Given the expanded stratigraphic interval (3.47–3.22 Ga) now sampled from across the Barberton Supergroup, we conclude that large MIF‐S exceeding >4‰ is atypical of Paleoarchean near‐surface environments on the Kaapvaal Craton. [ABSTRACT FROM AUTHOR]