Basalt-derived krasnozems are generally well-structured soils; however, there is a concern that intensive agricultural practices may result in an adverse decline in soil organic carbon, organic matter chemistry, and structural quality over time. A study was conducted on loam to silty clay loam krasnozems (Ferrosols) near Ballarat in south-western Victoria to assess changes in soil C, soil structural stability, and C chemistry, at the 0–10 cm soil depth, under 3 paired sites consisting of adjacent long-term forest (Monterey pine or eucalyptus) v. 30 year cropping [3 year pasture–2 year crops (potato and a root crop or grain)]. Soil structural stability was also characterised in the A and B horizons under long-term eucalyptus and several cropped sites. Organic C levels in the A horizons for all the soils were relatively high, ranging from 46 to 89 g/kg. A lower organic C (30%), associated mainly with loss of the sand-sized (>53 m) macro-C fraction, and a decrease in exchangeable Ca and Mg was found in the agricultural soils, compared with forest soils. Physically protected C in the 5 mm sized aggregates, with no deleterious increase in the proportion of 0.10 mm aggregates. Solid state 13C NMR spectroscopy indicated a decrease in O-alkyl and alkyl C under pasture and cropping compared with forest soils, which was in agreement with the decline in the macro-C fraction. Characterisation of C chemistry following UV photo-oxidation showed that charcoal C (dominant presence of aryl C) accounted for 30% of the total soil organic C, while other functional groups (polysaccharides and alkyl C) were probably protected within micro-aggregates. Based on soil organic C and aggregate stability determinations alone, the implications for soil physical quality, soil loss, and diffuse pollution appear minimal. macroorganic carbon, soil aggregation, charcoal, photo-oxidation, potato rotation, CP/MAS 13C NMR spectroscopy.