Low temperature curable benzoxazines are highly warranted due to the lower energy consumption and less energy output, which are essential for the fabrication of industrial composite products and insulation of low melting microelectronics components. The present work focuses on comprehensive analysis of four different N, N-dimethyl benzoxazine derived from phenol and dimethylaminomethylphenol with aniline, N, N-dimethyl substituted aniline. The structure-dependent benzoxazine monomers were confirmed using FTIR and 1H NMR analyses. The ring opening polymerization (ROP) behavior of all the developed benzoxazine monomers were assessed using DSC. The results show that the curing temperature of the N, N-dimethyl amino group containing benzoxazines were ranged between 205°C and 230°C. Among all monomers, P-d possess the lowest ROP of 205°C. The presence of N, N-dimethyl amino group in both amine and phenol precursors does not effectively reduces the ROP while, the presence of N, N-dimethyl amino group in amine moiety effectively reduces the ROP temperature. Further, two types of imidazolium ionic liquids such as MI (methyl-imidazolium iodide) and AI (amino-propyl-imidazolium iodide) were developed and structurally confirmed using FTIR and 1H NMR. Among them, MI catalyzed P-d shows the lowest curing temperature of 151°C, on the other hand AI catalyzed P-d possesses the curing temperature to 157°C. Kinetic analysis further confirmed that both monomer design and ionic liquid catalysis play crucial role in lowering Ea. Both MI and AI catalysts effectively alter the thermal stability and char yield of the polybenzoxazines. However, AI catalysed polybenzoxazines exhibited the lowest thermal stability and lowest char yield compared to those of MI catalysed polybenzoxazines. The results clearly show that the ionic liquid effectively influence and transforms the benzoxazine into low-temperature curable formulations, which is highly advantageous for coatings and warranted for substrate-sensitive applications.