An integrated process of CO₂ capture and in situ hydrogenation into formate was achieved in 95–99% yield using a tunable ethoxyl-functionalized amidine and Rh/bisphosphine system, being regarded as an alternative carbon capture and utilization approach to supply fuel-related products, to circumvent the energy penalty in carbon capture and storage. CO₂ was captured by non-volatile amidine derivatives with simultaneous activation to form zwitterionic amidinium carbonate, and subsequent hydrogenation was facilitated by Rh/bisphosphine. The adsorption capacity and hydrogenation efficiency can be optimized by tuning the ethoxyl side chain. Particularly, the alkanolamidine bearing an intramolecular hydrogen donor derived from 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) gave both a high CO₂ uptake (molar ratio of 0.95 : 1) and excellent hydrogenation yield (99%). Furthermore, the silica-supported alkanolamidine was readily recovered and reused with the retention of good performance. This kind of carbon capture and utilization pathway could be a potential energy-saving option for industrial upgrading of CO₂ from waste to fuel-related products in a carbon neutral manner.