A 2D NMR analysis was performed to examine the microstructure of Polyisobornyl Methacrylate (PiBMA) which was synthesized using Atom Transfer Radical Polymerization (ATRP) with a Copper(I) Bromide catalyst and PMDETA - N,N,N',N',N"-Pentamethyldiethylenetriamine ligand, as well as a methyl-2-bromopropionate (MBP) initiator. The complex 1H NMR spectra were resolved, and the stereo-sequences of PiBMA were established up to the diad level for β-CH2 carbons and up to the triad level for α-CH3 (C12) and carbonyl (C11) carbons using 2D HSQC as well as TOCSY NMR experiments. The 2D HMBC NMR spectra completely resolved the quaternary carbons in the 13C{1H} viz. the carbon observed, proton broadband decoupled NMR spectrum. The analysis revealed that the tacticity of PiBMA, estimated for the C11 carbon peaks, was arbitrary, with rr = 53%, mr = 42% and mm = 4%, which was similar to that of PiBMA prepared using AIBN as an initiator through free radical polymerisation.