4-Hydroxythiophenol (HTP) grafted poly(styrene-bacrylic acid) (PS-b-PAA) block copolymers (BCPs) (PS-b-PAA-gHTP) was synthesized using the esterification reaction between the carboxyl groups and hydroxyl groups. Self-assembly behavior of the graft copolymer in 1,4-dioxane/ water was investigated. Assemblies of different morphologies, porous, and bowl-shaped structures, could be easily prepared. A possible mechanism for the formation of the porous and bowlshaped structures was discussed. The present study showed a facile method for the preparation of functionalized PS-b-PAA BCPs, which could easily self-assembly into novel structures in aqueous solution. These assemblies may be used to generate new functional materials. (C) 2016 Wiley Periodicals, Inc.