The development and study of advanced methods to encapsulate and provide a controlled release of drugs and bioactive agents provide the opportunity to deliver active factors in situ. This acute delivery requires systems to be able to precisely control the release rate, however this has been challenging to achieve using a single component system. We developed novel Polycaprolactone (PCL) porous templates to control the release of encapsulated alginate hydrogel containing water-soluble molecules of different molecular weights. The presence of molecule-loaded alginate within the PCL porous templates was confirmed by infrared spectroscopy, fluorescence imaging and scanning electron microscopy. The influence of the molecular weight of the encapsulated molecule was investigated. The release profile of PCL-alginate displayed significant improvement on slowing the release of molecules of different molecular weight when compared with alginate alone. Based on the results, we can suggest that PCL porous templates can be a promising candidate to form composite delivery systems carrying high molecular weight hydrophilic agents for tissue engineering and drug delivery applications.