Nanostructure templates fabrication from P(S-b-MMA) thin films requires precise control of interfacial energies to achieve perpendicular orientation of microdomains to the substrate surface and can be obtained by modifying the oxide layer on silicon with a covalently anchored hydroxyl-terminated random copolymer P(S-r-MMA) termed a “neutral brush”. This commonly employed method enables precise fine-tuning of interfacial energies, but involves a lengthy process, requires starting materials that are commercially available but expensive, and results in a relatively thick under layer that can interfere with subsequent surface processing. We report here the microphase separation behaviour of an asymmetric P(S-b-MMA) diblock copolymer on electronic substrates modified with ethylene glycol (EG) self-assembled monolayer (SAM) as alternative to standard random copolymer brush. The diblock copolymer films deposited on EG SAMs upon thermal annealing spontaneously generates features with sub-lithographic resolution and pitch with perpendicular orientation. Selective etching provides a rapid route for the generation of PS template structures as the PMMA domains are etched at a faster rate. These templates can subsequently be used as etch masks to generate nanoscale features. We use state of the art lithography to generate sub-μm features and within these generate nm sized copolymer templates. Graphoepitaxy method proved a successful approach for the alignment of the microphase separated structures. This method of EG SAM driven self-0assembly provides a simple, rapid, yet tuneable approach for surface neutralization and nanofabrication technique for creating high density nanoscale features for the nanoelectronic industry.