Reforestation of agricultural land with mixed-species environmental plantings of native trees and shrubs contributes to abatement of greenhouse gas emissions through sequestration of carbon, and to landscape remediation and biodiversity enhancement. Although accumulation of carbon in biomass is relatively well understood, less is known about associated changes in soil organic carbon (SOC) following different types of reforestation. Direct measurement of SOC may not be cost effective where rates of SOC sequestration are relatively small and/or highly spatially-variable, thereby requiring intensive sampling. Hence, our objective was to develop a verified modelling approach for determining changes in SOC to facilitate the inclusion of SOC in the carbon accounts of reforestation projects. We measured carbon stocks of biomass, litter and SOC (0–30 cm) in 125 environmental plantings (often paired to adjacent agricultural sites), representing sites of varying productivity across the Australian continent. After constraining a carbon accounting model to observed measures of growth, allocation of biomass, and rates of litterfall and litter decomposition, the model was calibrated to maximise the efficiency of prediction of SOC and its fractions. Uncertainties in both measured and modelled results meant that efficiencies of prediction of SOC across the 125 contrasting plantings were only moderate, at 39–68%. Data-informed modelling nonetheless improved confidence in outputs from scenario analyses, confirming that: (i) reforestation on agricultural land highly depleted in SOC (i.e. previously under cropping) had the highest capacity to sequester SOC, particularly where rainfall was relatively high (> 600 mm year− 1), and; (ii) decreased planting width and increased stand density and the proportion of eucalypts enhanced rates of SOC sequestration. These results improve confidence in predictions of SOC following environmental reforestation under varying conditions. The calibrated model will be a useful tool for informing land managers and policy makers seeking to understand the dynamics of SOC following such reforestation.