We study two metal-free catalysts for the reduction of CO2 with four different hydroboranes and try to identify mechanistically relevant intermediate species. The catalysts are the phosphinoborane Ph2P(CH2)(2)BBN (1), easily accessible in a one-step synthesis from diphenyl(vinyl)phosphine and 9-borabicyclo[3.3.1]-nonane (H-BBN), and its formaldehyde adduct Ph2P(CH2)(2)BBN(CH2O) (2), detected in the catalytic reduction of CO2 with 1 as the catalyst but properly prepared from compound 1 and p-formaldehyde. Reduction of CO2 with H-BBN gave mixtures of CH2(OBBN)(2) (A) and CH3OBBN (B) using both catalysts. Stoichiometric and kinetic studies allowed us to unveil the key role played in this reaction by the formaldehyde adduct 2 and other formaldehyde-formate species, such as the polymeric BBN(CH2)(2)(Ph2P)(CH2O)BBN(HCO2) (3) and the bisformate macrocycle BBN(CH2)(2)(Ph2P)(CH2O)BBN(HCO2)BBN(HCO2) (4), whose structures were confirmed by diffi-actometric analysis. Reduction of CO2 with catecholborane (HBcat) led to MeOBcat (C) exclusively. Another key intermediate was identified in the reaction of 2 with the borane and CO2, this being the bisformaldehyde-formate macrocycle (HCO2){BBN(CH2)(2)(Ph2P)(CH2O)}(2)Bcat (5), which was also structurally characterized by X-ray analysis. In contrast, using pinacolborane (HBpin) as the reductant with catalysts 1 and 2 usually led to mixtures of mono-, di-, and trihydroboration products HCO(2)Bpin (D), CH2(OBpin)(2) (E), and CH(3)OBpin (F). Stoichiometric studies allowed us to detect another formaldehyde-formate species, (HCO2)BBN(CH2)(2)(Ph2P)(CH2O)Bpin (6), which may play an important role in the catalytic reaction. Finally, only the formaldehyde adduct 2 turned out to be active in the catalytic hydroboration of CO2 using BH3 center dot SMe2 as the reductant, yielding a mixture of two methanol-level products, [(OMe)BO](3) (G, major product) and B(OMe)(3) (H, minor product). In this transformation, the Lewis adduct (BH3)Ph2P(CH2)(2)BBN was identified as the resting state of the catalyst, whereas an intermediate tentatively formulated as the Lewis adduct of compound 2 and BH3 was detected in solution in a stoichiometric experiment and is likely to be mechanistically relevant for the catalytic reaction.