Summary: The possibility of applying basic aluminum carboxylates as the crosslinking monomers in radical polymerization processes as well as the initiators for ATRP of styrene and coordination ROP of heterocyclic monomers was examined. It was established, that aluminum carboxylates containing in their structure the acrylic and lauric acids derivatives show high activity in the copolymerization with vinyl monomers which results in the hybrid polymer networks formation. In the typical ATRP conditions, polymers grafted with styrene are obtained while basic aluminum 2-bromopropionate is used as the initiator. Hybrid composites i.e. core-shell nanospheres can be obtained in this way at low degree of polymerization. Nanoparticles of basic aluminum caroboxylates when reacted with triethylaluminum show high activity as initiators in the polymerization processes of e-caprolactone, trimethylene carbonate as well as propylene and ethylene oxides. Cross-linked products in the form of a gel were formed as the result of ROP in such systems. However, linear polymers characterized by M n above 10 4 and PDI ! 1.9 were obtained after aluminum residuals removal.