The mechanism of CO absorption by a formate ionic liquid, [P ]HCOO, was studied by Raman spectroscopy. The band area for the symmetric CO stretching of the formate anion linearly decreases with the CO loading. From the slope of the decrease, 1 : 1 stoichiometry is proven between CO and the formate anion. The result favors the mechanism we proposed in a preceding work [J. Chem. Eng. Data 61, 837 (2016)]: HCOO +CO +H O→HCOOH+HCO →[HCOOH…HCO ]. Further support for the mechanism is obtained by the observation of antisymmetric vibration of CO for the proposed hydrogen-bonded complex between HCOOH and HCO . The bands appeared as a doublet (1677 and 1730 cm ) as this complex has two carbonyl groups. Based on DFT calculations, the [HCOOH…HCO ] complex is supposed to be the most abundant form of chemisorbed CO .