A new type of self-assembled PMMA/aramid nano-blends were developed from an aromatic polyamide obtained by condensing 4,4'-oxydianiline with isophthaloyl chloride. Physical interactions between the two polymers derived molecular self-assembly process, ensuing marvelous nano-structured blends. Exclusive nano-scale morphology generated in perfectly miscible PMMA/aramid blends was studied using FESEM. Moreover, the effect of blend nano-structure and N-H/C=O interactions between the components on T (g), thermal, tensile and crystalline behavior were investigated. Addition of aramid imparted mechanical and thermal stability to novel blends owing to the physical interlocking of PMMA and polyamide chains via hydrogen bonding. As a result 40- and 70-wt% aramid-containing blends demonstrated fine morphological profile complemented by the optimal mechanical reinforcement and high temperature resistance. In future new blends, holding excellent properties due to physical interaction between the components, can be exploited to acquire exceptional performance in various technological applications such as nano-devices.