A set or dendritic-linear copolymers, poly(glycidyl methacrylate-grafted-dimethyl 3,3'(4-hydroxyphenylazanediyl)bis(2-methylpropanoate))-random-polystyren e (PGMA-HPAM-r-PS), were successfully prepared by copolymerization of the novel dendritic macromonorner dimethyl 3,3'-(4-(2-hydroxy-3-(methacryloyloxy)propoxy)phenylazanediyl)bis(2-meth ylpropanoate) (GMA-HPAM) and a styrene monomer. The dendritic GMA-HPAM macromonomer dendron 3,3'-(4-hydroxyphenylazanediyl) bis(N-(2-aminoethyl)2-methylpropanamide (HPAM) was then grafted using the divergent growth method. H-1 NMR and C-13 NMR spectra Were used to identify the structure of the dendritic-linear GMA-HPAM-r-PS copolymer. Microporous dendritic-linear PGMA-HPAM-r-PS copolymer films in this system were prepared by using solvent-induced phase separation at room temperature. The phase separation behavior and the morphological analyses of the dendritic-linear copolymer film as functions of dendritic GMA-HPAM segment contents were investigated by using A FM, TEM, and SEM. Self-assembly of the dendritic-linear PGMA-HPAM-r-PS copolymer in a G2-37 system containing 37 wt % or the dendritic GMA-HPAM segment, which exhibits the second generation dendron, showed submicrometer phase segregation with the main chain styrene segment. Interestingly, the submicrometer phase segregation morphology of the G2-37 sample represented a uniform size distribution of the hexagonally ordered structures. Our results prove that controlling the appropriate macromonorner content by grafting a three-dimension structure results in self-assembly and provides a honeycomb ordered microporous copolymer matrix.