Titanium dioxide (TiO2) is widely used to purify air pollutants in environmental engineering, but it is only activated by ultraviolet (UV) light. To broaden the spectral response range of TiO2 to further increase the photocatalytic activity and purification efficiency on vehicle exhaust under visible light, Fe-doped TiO2 is loaded on the biomass activated carbon (AC) to prepare the composite photocatalyst (Fe-TiO2/ AC). Then Fe-TiO2/ AC substituted part of fine aggregates in asphalt mixture of open-graded friction course-16 (OGFC-16) for degrading vehicle exhaust (VE). Results indicates that Fe is doped into crystal lattices of TiO2 in the predominant form of Fe3+ to substitute for Ti4+, leading to surface defects, lattice distortion and distortion in the crystal structures of TiO2. The generated non-lattice oxygen due to the Fe doping has a stronger attraction to adsorbed oxygen and hydroxyl, improving the photocatalytic activity of TiO2. Additionally, the reflectance edge of Fe-doped TiO2 shows an obvious red shift to visible light region with the maximum wavelength of 550 nm. This increases the utilization ratio of visible light irradiation of TiO2, broadening the spectral response range of TiO2. Further, HC and NOx in VE are obviously degraded by OGFC-16 under visible light irradiation because of the synergy between the Fe-doped TiO2 degradation and AC adsorption. The photocatalytic efficiency of OGFC-16 to HC and NOx are improved when the Fe-TiO2/AC content is increased. However, there is a reversible reaction between CO2 and CO during their photocatalytic degradations. Thus, OGFC-16 asphalt mixture shows lower photocatalytic efficiency to CO and CO2. Finally, the Fe-TiO2/AC replacement percentage of 60% is proposed to replace the fine aggregate in OGFC-16 asphalt mixture, which occupies 3.34% in OGFC-16, improving its pavement properties, developing a green and sustainable pavement material.