The effect of chain-end chemistry on surface and interfacial segregation in symmetric blends of polystyrene (hPS)/deuterated polystyrene (dPS) has been investigated by X-ray photoelectron and secondary ion mass spectroscopy in conjunction with neutron reflectivity measurements. alpha,omega-Fluoroalkyl- and alpha,omega-carboxy-terminated polystyrenes (alpha,omega-hPS(R-f)(2) and alpha,omega-hPS(COOH)(2)) were used as end-functionalized polymers; the former possesses chain ends with lower surface energies, and the latter possesses higher surface energies compared with that of the main chain. In the case of an alpha,omega-hPS(R-f)(2)/dPS blend film, alpha,omega-hPS(R-f)(2) was enriched at the surface owing to the surface localization of the R-f groups, although the surface energy of the hPS segments was slightly higher than that of the dPS ones. On the contrary, in the case of an alpha,omega-hPS(COOH)(2)/dPS blend film, dPS was preferentially segregated at the surface. This may be due to a surface depletion of COOH ends and an apparent molecular weight increase of alpha,omega-hPS(COOH)(2) produced by a hydrogen-bonded intermolecular association of COOH ends in addition to the surface energy difference between hPS and dPS segments. Interestingly, both R-f and COOH chain ends were partitioned to the substrate interface for the alpha,omega-hPS(R-f)(2)/dPS and alpha,omega-hPS(COOH)(2)/dPS blend films, resulting in the segregation of the hPS component at the substrate interface for both blends. The results presented imply that surface and interfacial segregation in polymer blends could be regulated by incorporating functional groups into the end portions of one component.