Abstract In this study Rubitherm-RT5®, a PCM with a phase transition temperature around 5 °C, was encapsulated inside PCL, PLA and PS by means of electrohydrodynamic processing in order to develop thermal energy storage systems for refrigeration applications. The effect of the morphology of the encapsulation structures (fibrillar or spherical) on thermal properties and encapsulation efficiency was evaluated. The morphology of the structures played an important role on the energy storage capacity, since PCM was better encapsulated in fibrillar structures, providing higher energy storage capacity. The greater encapsulation efficiency was achieved for the fibers, which showed that ~ 80–90 wt.% of the incorporated PCM, effectively remained within the polymeric matrices. These hybrid structures are of great interest for the development of active packaging systems aimed at improving food quality preservation under refrigeration conditions. Industrial relevance As a response to the consumers for more safety foodstuffs and low environmental impact technologies, this work presents a novel methodology to develop energy storage materials. These materials buffer thermal variations and, thus, could be used in packaging systems to better preserve the cold chain. Furthermore, the incorporation of these materials in refrigeration equipment could reduce energy consumption of existing refrigeration technologies.