The internal phase separation technique is a versatile method for liquid core-polymer shell formation, yet limited to very hydrophobic core materials and actives. The use of polymeric cores instead circumvents this restriction due to the absent mixing entropy for binary polymer mixtures which allows the polymeric core (and the active) to approach the polarity of the shell. Polystyrene core-shell and janus particles were formulated using polymethylmethacrylate, poly(lactic acid), poly(lactic acid-co-glycolic acid), poly(ε-caprolactone) or cellulose triacetate as shell-forming polymers. The morphology and the partitioning was experimentally determined by selectively staining the core and the shell with β-carotene and methylene blue respectively. In addition, the van Oss formalism was introduced to theoretically predict the thermodynamic equilibrium morphology. As elucidated using the theoretical predictions as well as experimental optical tensiometry, it was found that the driving force for core-shell morphology is, in contrast to liquid core-polymer shell particles, a low core-shell interfacial tension.