A novel hyperbranched polymeric ionic liquid (HBP-AMIM(+) PF6(-)) was explored via a thiol-ene click reaction using thiol-ended hyperbranched polyesters (THBP) and 1-allyl-3-imethylimidazolium hexafluorophosphate (AMIMPF6). The effects of HBP-AMIM(+) PF6(-) on the curing behavior, mechanical properties and thermal stability of benzoxazine/epoxy thermosets were investigated. The gelation time and differential scanning calorimetry of non-isothermal analysis indicated that the addition of HBP-AMIM(+)PF6(-) significantly decreased the curing temperature of benzoxazine/epoxy thermosets. Simultaneously, the addition of HBP-AMIM(+)PF6(-) also improved the strength, toghness and thermal properties of benzoxazine-epoxy thermosets. The addition of 3 wt% HBP-AMIM(+) PF6(-) -2 could significantly improve the mechanical and thermal performance of thermosets compared with that of cured neat benzoxazine/epoxy resin. The tensile strength, tensile toughness, flexural strength and flexural modulus, impact strength of the thermosets were improved by about 76.6%, 279.3%, 57.8%, 22.3% and 80.4%, respectively, compared with those of cured neat resin. The toughening mechanisms was attributed to the "in situ" reinforcing and toughening mechanism.