Phase change materials (PCM) have gained extensive attention in thermal energy storage applications. In this work, microencapsulation of vegetable-derived palmitic acid (PA) in bio-based polylactic acid (PLA) shell by solvent evaporation and oil-in-water emulsification was investigated. Fourier transform infrared spectroscopy and scanning electron microscopy were conducted to confirm the successful encapsulation of PA in PLA shells. Differential scanning calorimetry was performed to evaluate the thermal properties, thermal reliability, and core content of the fabricated PCM microcapsules (microPCM). Through a series of parametric studies, the effects of PCM and solvent content, oil phase-to-aqueous phase ratio, as well as surfactant type and content on the morphology, particle size, and thermal properties of the PCM microcapsules were investigated. Experimental results showed that PVA was a superior emulsifier to SDS in the emulsion systems being studied. There also existed an optimal PVA concentration to reduce the average size of microPCM. When the PVA concentration was above this optimal level, the emulsifier molecules tend to form micelles among themselves. This led to the adhesion of tiny microspheres on the surface of microPCM as well as larger microPCM. In short, this work has demonstrated the possibility of using the solvent evaporation method to fabricate 100% bio-based PCM-polymer microcapsules for thermal energy storage applications.