Current approaches of mixing fuel and oxidizer nanoparticles or adding fuel nanoparticles to oxidizer gel lead to an overall reduced interfacial area of contact between them and thus, limit their burn rates severely. We have developed an approach of self-assembling fuel nanoparticles around an oxidizer matrix using a monofunctional polymer, poly(4)-vinyl pyridine (P4VP). The polymer has been used to accomplish binding of fuel and oxidizer in a molecularly engineered manner. We use composite of Al-nanoparticles and CuO nanorods for executing this self-assembly. TEM images of this composite confirms the self-assembly of Al-nanoparticles around the oxidizer nanorods. The burn rate of self-assembled composite has been found significantly higher than that of the composite prepared by simple mixing.