5,10,15,20-tetra(4-hydroxyphenyl)porphyrin (THPP) was synthesized by the condensation of pyrrole with 4-hydroxybenzaldehyde in the presence of solvent (propionic acid). Subsequently, the resulting THPP was converted to a tetrafunctional star-shaped macroinitiator (porphyrin-Br4) by esterification of it with 2-bromopropanoyl bromide, and then atom transfer radical polymerization (ATRP) of styrene was conducted at 110 degrees C with CuCl/2,2'-bipyridine as the catalyst system. The resulting product was reacted with NBS to obtain star-shaped initiator porphyrin-(PSt-Br)4, which was used the following ATRP of the GMA to synthesize starcomb-shaped grafted polymer porphyrin-(PSt-g-PGMA)4. The number molecular weight was 2.3 x 104 g/mol, and the dispersity was narrow (Mw/Mn = 1.32). The structure of the polymers was investigated by NMR, UVvis, IR, and GPC measurement. The self-assembly behavior of the polymer porphyrin-(PSt-g-PGMA)4 was studied by DLS and AFM. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012