Macromolecular crowding plays a key role in liquid-phase condensation of proteins and membraneless organelles yet is largely unexplored for artificial liquid materials. Herein, we present a strategy for direct access to multiphase liquid condensates with individual charged/neutral subdomains, by introducing macromolecular crowding to our previous protocol of liquid-liquid phase-separation-driven polymerization-induced electrostatic self-assembly (LLPS-PIESA). We show that reversible addition fragmentation chain transfer (RAFT) aqueous dispersion photo-copolymerization of a charged monomer with a specific neutral monomer, in the presence of a polar macrochain transfer agent (CTA) and an oppositely charged polyion, can induce self-sorting and macromolecular crowding. LLPS-PIESA proceeds via liquid-phase condensation of as-assembled nascent clusters up to biologically important nanostructured multiphase condensates with individual charged/neutral subdomains.