A study of a top-down technique of nanoimprint lithography (NIL) for developing a novel bottom-up approach of chemical vapor deposition to generate anti-adhesive coatings between Ni mold stamps and polymethyl methacrylate (PMMA ) substrate is presented in this work. A polybenzoxazine ((6,6'- bis(2,3-dihydro-3-methyl-4H-1,3-benzoxazinyl))) molecule selfassembled monolayer (PBO-SAM) regarded as an anti-adhesive coating agent demonstrates that non-fluorine-containing compounds can improve the nanoimprint process in Ni/PMMA substrates. In this experiment, the nanostructure-based Ni stamps and imprinted PMMA molds are fabricated using an electronbeam lithograph (EBL) and a homemade nanoimprint equipment, respectively. The diameter of pillar patterns obtained is 200 nm with 400 nm pitch on Ni stamp surface. Based on the hydrophobic PBO-SAM surface in this forming condition, the results of Ni mold stamps indicate over 90% improvement in controlling quality and quantity.