The activated carbon fibres (ACF), with a proprietary surface modified by the solution of palladium chloride (PdCl2), cuprous chloride (CuCl) and graphite oxide (GO) separately, were analysed by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The changes in the physical and chemical properties of the ACF surface after modification were characterised in terms of specific surface area, pore distribution and functional group content. The deliveries of tar, carbonyl and phenolic compounds in mainstream smoke of cigarettes with a filter containing ACF were determined. The results showed that: firstly, the absorption characters of ACF were modified by PdCl₂, CuCl or GO and were significantly improved with the changes of specific surface area, pore structure and surface chemical property. Secondly, the delivery of tar in mainstream smoke of all samples with an ACF-containing filter decreased to some extent. The ACF treated by PdCl₂/CuCl (Pd²⁺/Cu⁺-ACF) possessed a significant selective removal efficiency for phenolic compounds, the reduction rates for tar, phenol and catechol were 8.3%, 22.7% and 35.7%, respectively compared to the control; while the selective removal effect of Pd²⁺/Cu⁺-ACF on carbonyl compounds was not obvious. Thirdly, ACF treated by GO (GO-ACF) presented a significant selective filtration efficiency for carbonyl and phenolic compounds, the reduction rates for tar, phenol, catechol and crotonaldehyde were 8.3%, 28.3%, 18.0% and 33.4%, respectively, compared with the control. Fourthly, the reduction rates of carbonyl and phenolic compounds were independent of the specific surface area, and they were mainly affected by the changes in chemical properties of the ACF surface.