Stacking fault energy dictates phase stability and deformation behavior in Co alloys and WC-Co cemented carbides, yet a quantitative assessment of alloying effects at finite temperatures remains poorly established. By integrating first-principles thermodynamics with microstructural characterization, we provide a rigorous evaluation of these influences across atomic and macroscopic scales. We show that stacking fault energetics at 0 K for transition metal solutes are primarily governed by atomic misfit volume. While 4d and 5d elements follow a consistent linear trend, specific 3d solutes exhibit significant deviations due to non-negligible magnetic contributions. By incorporating phonon, electronic, longitudinal spin-fluctuation, and magnetic free-energy contributions, the model accurately captures the fcc-hcp transformation and quantifies how diverse solutes modulate the phase landscape. We demonstrate that V, Mn, Mo, and W lower the transformation temperature by stabilizing the fcc phase, whereas Cr and C exhibit the opposite effect. Fe and Ni show comparatively weaker effects at dilute concentrations. Furthermore, microscopic observations are qualitatively consistent with the predicted increase in stacking fault energy with W addition at finite temperatures. This work clarifies the physical mechanisms by which alloying regulates stacking fault energy and phase stability in Co-based systems, providing guidance for the design of Co-based alloys and WC-Co cemented carbides.