We have synthesized poly(methyl methacrylate-b-4-vinylpyridine) (PMMA-b-P4VP) and poly (styrene-r-vinylphenol) (PS-r-PVPh) copolymers by using anionic and free radical polymerizations, respectively. Well-defined micelles through hydrogen bonding have been prepared by mixing PMMA-b-P4VP diblock copolymer and PS-r-PVPh random copolymer in a single solvent. Block copolymers were mixed with random copolymers, with various [N]/[OH] ratios (4/1, 2/1, 1/1, and 1/4) in which "[N]/[OH]" represents the molar ratio of pyridine groups on P4VP to hydroxyl groups on PVPh. The presence distribution of PVPh/P4VP and PVPh/PMMA hydrogen bonding depends on the feeding ratio of PVPh to P4VP. When the PVPh content is lower than that of P4VP, hydrogen bonding occurs only between PVPh and P4VP; with excess PVPh, additional hydrogen bonding between PVPh and PMMA would occur. Furthermore, the effect of the solvent quality on the self-assembly behavior of PMMA-b-P4VP/PS-r-PVPh blends is investigated by considering tetrahydrofuran (THF) and dimethylformamide (DMF) as common solvents. We can mediate the strength of hydrogen bonding in blend systems by adopting different solvents and inducing different morphology transitions.