AbstractPolymerization induced self‐assembly (PISA) is an in situ method for producing block copolymer nanoparticles. Performing PISA in the presence of a pharmaceutical drug causes the nanoparticles to encapsulate the drug. While this approach is straightforward, the effects of drug loading and block copolymer composition remain unclear. Here, we investigate encapsulation of the drug phenylacetic acid (PA) in poly(glycerol monomethacrylate)‐block‐poly(2‐hydroxypropyl methacrylate) (PGMA‐PHPMA) nanoparticles during PISA. Nanoparticle morphology is characterized by electron microscopy and light scattering, while encapsulation efficiency () is quantified using nuclear magnetic resonance diffusometry. Increasing the PA loading shifts the nanoparticle morphology from spherical micelles cylindrical micelles vesicles. At a 32 mg/ml PA loading, maximizes at ~80%. Increasing the PHPMA degree of polymerization minimally impacts . The invariance of toward core block length suggests that PA binds to the nanoparticle corona, highlighting the importance of the hydrophilic block for drug encapsulation during PISA.