Atomically dispersed transition metal sites on nitrogen-doped carbon catalysts hold great potential for the electrochemical CO2 reduction reaction (CO2RR) to CO due to their encouraging selectivity. However, their intrinsic activity is restricted by the hurdle of the high energy barrier of either *COOH formation or *CO desorption due to the scaling relationship. Herein, we discover a p-block aluminum single-atom catalyst (Al-NC) featuring an Al-N4 site that enables disentangling this hurdle, which endows a moderate reaction kinetic barrier for *COOH formation and *CO desorption, as validated by in situ attenuated total reflection infrared spectroscopy and theoretical simulations. As a result, the developed Al-NC shows a CO Faradaic efficiency (FECO) of up to 98.76% at -0.65 V vs RHE and an intrinsic catalytic turnover frequency of 3.60 s-1 at -0.99 V vs RHE, exceeding those of the state-of-the-art Ni-NC and Fe-NC counterparts. Moreover, it also delivers a partial CO current of 309 mA·cm-2 at 93.65% FECO and 605 mA at >85% FECO in a flow cell and membrane electrode assembly (MEA), respectively. Strikingly, when using low-concentration CO2 (30%) as the feedstock, this catalyst can still deliver a partial CO current of 240 mA at >80% FECO in the MEA. Considering the earth-abundant character of the Al element and the high intrinsic activity of the Al-NC catalyst, it is a promising alternative to today's transition metal-based single-atom catalysts.