This study is interested in the effect of lithium carbonate on the formation of hexagonal boron nitride (hBN) by means of the available experimental methods including TGA, XRD, FTIR, SEM and HR-TEM. hBN samples were synthesized at the 1450°C with different molar ratios of lithium carbonate by modified O'Connor routine. The crystalline hBN formation tended to improve with the increment of the Li 2 CO 3 concentration level (especially after more 20 %). The dopant quantity decreased the residual stresses due to the presence of possible relaxation mechanisms along with the nanocrystal structure, even favored by XRD experimental findings regarding the enhancement of crystal plane alignments, crystallite sizes and lattice parameters. As for the FTIR surveys, the Li 2 CO 3 foreign impurities strengthened more and more the covalent bonds between boron and nitrogen atoms. At the same time, the samples with 40 % lithium carbonate were annealed at the varied temperatures of 1000, 1150, 1300 and 1450°C to determine the optimum annealing temperature. The XRD+FTIR investigations indicated that the degree of hexagonality improved with the increased annealing temperature. Similarly, the surface morphology confirmed not only the formation of regularity and flaky hexagonal BN structures, but also the strengthening of covalent bonds between the atoms.