Decarbonising road transport using on-board carbon capture and storage (CCS) is challenged by inherent space and energy limitations. Thus, to be technically and economically viable, robust and compact carbon capture units need to be developed. Hence, in this work, a scaled up hollow fibre adsorption unit was tested downstream of a real 90:10 gasoline-ethanol engine exhaust gas to evaluate its CO2 capture performance after 100 adsorption–desorption cycles. The scaled up hollow fibre adsorption unit consisted of 37 four-channel hollow fibre adsorption units coated with a thin carbon xerogel layer, referred to as the CX-coated hollow fibre module (HFM). It should be noted that this is the first study to report the results of a HFM tested under real conditions over 100 adsorption–desorption cycles and is one of the few studies that reports the desorption step. Furthermore, despite the presence of CO, THC, NOx, and H2O in the exhaust gas, the CX-coated HFM exhibited high CO2 capture stability and mechanical integrity. This was evidenced through the CX-coated HFM obtaining and maintaining an average total capacity of 1.2 mmol/g over 100 adsorption–desorption cycles, and showing no visible signs of deterioration or a loss of mechanical integrity.