The curing of bisphenol A-aniline based benzoxazine was studied applying different accelerators (4,4'-thiodiphenol, o-dianisidine, 2-mercaptobenzimidazole and 4-mercaptophenol) to initiate the catalytic ring-opening of benzoxazine. Possible pathways of benzoxazine ring-opening, polymerization and cross-linking without and with the addition of different accelerators are presented. The curing kinetics was investigated by model-free kinetic analysis of experimental data obtained by differential scanning calorimetry (DSC). The addition of different accelerators significantly reduced the onset temperature of curing in dynamic experiments. The effects of accelerators on the results of isothermal conversion prediction were studied and discussed in detail. Among the used accelerators, thiodiphenol showed the best accelerating efficiency and was consequently used in further studies, where its amount was varied. By low heating rate DSC analysis the catalytic ring-opening, thermally accelerated ring-opening and the diffusion-controlled steps were identified. The amount of added accelerator affected particularly the ring-opening and diffusion-controlled steps.