In this work, we have demonstrated how an enzymatic reaction can induce the formation of new-to-nature polymeric vesicles, which can be equipped to increasing levels of complexity, from simple vessels to microreactors and full cell mimics capable of producing their own proteins, thanks to the co-encapsulated plasmids as genetic information. For the first time, an enzyme could self-encapsulate within an unnatural membrane it synthesized, entrapping all the complex components deriving from cell lysates, which in turn could express specific proteins and modify the structure of the vesicles, producing internal compartments, or transforming them into polymer-mineral hybrids. Cell mimics were produced in the most bio-similar process possible, showcasing the versatility and robustness of bioCRP. Moreover, bioPISA proved to be a very efficient and biocompatible encapsulation method for a range of cargo. Our findings will pave the way for novel hybrid systems combining synthetic polymers with the diversity of natural molecules, offering a plethora of applications in synthetic biology, sensing, catalysis and biomaterials.