Sustainable intensification schemes such as integrated soil fertility management (ISFM) are a proposed strategy to close yield gaps, increase soil fertility, and achieve food security in sub-Saharan Africa. Biogeochemical models such as DayCent can assess their potential at larger scales, but these models need to be calibrated to new environments and rigorously tested for accuracy. Here, we present a Bayesian calibration of DayCent, using data from four long-term field experiments in Kenya in a leave-one-site-out cross-validation approach. The experimental treatments consisted of the addition of low- to high-quality organic resources, with and without mineral nitrogen fertilizer. We assessed the potential of DayCent to accurately simulate the key elements of sustainable intensification, including (1) yield, (2) the changes in soil organic carbon (SOC), and (3) the greenhouse gas (GHG) balance of CO2 and N2O combined. Compared to the initial parameters, the cross-validation showed improved DayCent simulations of maize grain yield (with the Nash–Sutcliffe model efficiency (EF) increasing from 0.36 to 0.50) and of SOC stock changes (with EF increasing from 0.36 to 0.55). The simulations of maize yield and those of SOC stock changes also improved by site (with site-specific EF ranging between 0.15 and 0.38 for maize yield and between -0.9 and 0.58 for SOC stock changes). The four cross-validation-derived posterior parameter distributions (leaving out one site each) were similar in all but one parameter. Together with the model performance for the different sites in cross-validation, this indicated the robustness of the DayCent model parameterization and its reliability for the conditions in Kenya. While DayCent poorly reproduced daily N2O emissions (with EF ranging between -0.44 and -0.03 by site), cumulative seasonal N2O emissions were simulated more accurately (EF ranging between 0.06 and 0.69 by site). The simulated yield-scaled GHG balance was highest in control tre