A set of dendritic-linear copolymers, poly(maleic anhydride-grafted-3,3'-dimethyl-(4-aminophenylazanediyl)bis(2-methylpropanoate))-random-polystyrene (PMA-APM-r-PS), was successfully prepared by copolymerization of the novel dendritic macromonomer, 4-(4-(bis(3-(4-(bis(3-methoxy-2-methyl-3-oxopropyl)amino)phenylamino)-2-methyl-3-oxopropyl)amino)phenyl- amino)-4-oxobut-2-enoic acid (MA-APM), with styrene monomer. The dendritic MA-APM macromonomer dendron 3,3'-di-methyl-(4-aminophenylazanediyl)bis(2-methylpropanoate) (APM) was then grafted by using the divergent growth method. FTIR, H-1 NMR, and C-13 NMR spectra were used to identify the structures of the dendron, the dendritic macromonomer, and the dendritic-linear PMA-APM-r-PS copolymer. Furthermore, microporous dendritic-linear PMA-APM-r-PS co-polymer films were prepared by using solvent-induced phase separation at room temperature. We investigated the phase separation behavior and morphological structures of the dendritic-linear copolymer film as functions of dendritic GMA-HPAM segments in the content using SEM. Self-assembly of the dendritic-linear PMA-APM-r-PS copolymer in the MG2-X system, which represented the second generation dendron containing X wt % of the dendritic MA-APM segment, resulted in submicron phase segregation. Interestingly, the submicron phase segregation morphology of the MG2-43 sample presented a uniform size distribution of ordered-array structures. The results of this study demonstrate that controlling the appropriate macromonomer content via the grafting of a three-dimensional structure results in a self-assembly process that is capable of providing an ordered-array microporous morphology in a polymer film. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3290-3301, 2010