Carbon dioxide (CO2) adsorption capacities of several Prussian Blue (PB) analogues have been studied using the state-of-the-art Rubotherm® sorption apparatus to obtain adsorption and desorption isotherms of these compounds up to 50 bar. The analogues were prepared by simply reacting a [M(CN)6]3- (M= Co, Fe) solution with solutions of M2+ (M= Mn, Fe, Co, Ni, Cu) metal ions. Characterization of the studied samples has been performed by using a combination of powder XRD, TGA, FTIR, and CHN elemental analysis. Adsorption capacities of PB analogues calculated with theoretical calculations, using Monte Carlo approach, have also been compared with the experimental study, and used to discuss the molecular mechanism of adsorption.