Polymerization-induced self-assembly of homopolymer and diblock copolymer using a binary mixture of small chain transfer agent (CTA) and macromolecular chain transfer agent (macro-CTA) is reported. With this system, homopolymer and diblock copolymer were formed and chain extended at the same time to form polymer nano-objects. The molar ratio of homopolymer and diblock copolymer had a significant effect on the morphology of the polymer nano-objects. Porous vesicles, porous nanospheres, and micron-sized particles with highly porous inner structure were prepared by this method. We expect that this method will greatly expand the promise of polymerization-induced self-assembly for the synthesis of a range of polymer nano-objects with unique morphologies.