Precipitation in microalloyed steel has been studied by applying thermodynamic calculations based on a description of the Gibbs energies of the individual phases over the full multicomponent composition range. To validate and improve the thermodynamic description, new experimental investigations of the phase separation in the cubic carbides/nitrides/carbonitrides in alloys containing Nb, V, Mo, and Cr, have been performed. Model alloys were designed to obtain equilibrium carbides/carbonitrides that are sufficiently large for measurements of compositions, making it possible to study the partitioning of the elements into different precipitates, showing distinctly different composition sets. The reliability of the calculations, when applied to multicomponent alloys, was tested by comparing with published experimental studies of precipitation in microalloyed steel. It is shown that thermodynamic calculations accurately describe the observed precipitation sequences. Further, they can reproduce several important features of precipitation processes in microalloyed steel such as the partitioning of Mo between matrix and precipitates and the variation of precipitate compositions depending on precipitation temperature.