The stepwise catalytic reduction of carbon dioxide (CO2) to formic acid, formaldehyde, and methanol opens non-fossil pathways to important platform chemicals. The present article aims at identifying molecular control parameters to steer the selectivity to the three distinct reduction levels using organometallic catalysts of earth-abundant first-row metals. A linear scaling relationship was developed to map the intrinsic reactivity of 3d transition metal pincer complexes to their activity and selectivity in CO2 hydrosilylation. The hydride affinity of the catalysts was used as a descriptor to predict activity/selectivity trends in a composite volcano picture, and the outstanding properties of cobalt complexes bearing bis(phosphino)triazine PNP-type pincer ligands to reach the three reduction levels selectively under different reaction conditions could thus be rationalized. The implications of the composite volcano picture were successfully experimentally validated with selected catalysts, and the challenging intermediate level of formaldehyde could be accessed in over 80% yield with the cobalt complex 6. The results underpin the potential of tandem computational-experimental approaches to propel catalyst design for CO2-based chemical transformations.