The efficient transformation of CO2 into chemicals and fuels is a key challenge for the decarbonisation of the synthetic production chain. Formic acid (FA) represents the first product of CO2 hydrogenation and can be a precursor of higher added value products or employed as a hydrogen storage vector. Bases are typically required to overcome thermodynamic barriers in the synthesis of FA, generating waste and requiring post-processing of the formate salts. The employment of buffers can overcome these limitations, but their catalytic performance has so far been modest. Here, we present a methodology utilising IL as buffers to catalytically transform CO2 into FA with very high efficiency and comparable performance to the base-assisted systems. The combination of multifunctional basic ionic liquids and catalyst design enables the synthesis of FA with very high catalytic efficiency in TONs of >8*105 and TOFs > 2.1*104 h-1.