New thermosetting resins with better integrated performances and easier processing characterization have been increasingly required by cutting-edge industries and energy-saving development. Herein, new high performance thermosetting resin was developed through building crosslinked network based on cyanate ester (CE) resin and a novel graphene oxide (GO) hybridized with manganese-Schiff base (MSG). The reactivity, crosslinked structure and comprehensive performances of MSG/CE resins were systematically studied. Compared with GO, MSG has better dispersion in CE resin, and a small addition of MSG (0.25 wt%) into CE significantly reduces the whole curing temperatures with a magnitude of 314-190 degrees C. This is because MSG uniquely integrates active hydrogen and manganese ions, and thus forms metal-it intermediates, which shows attractive catalysis on curing CE. Simultaneously, compared with CE resin, MSG/CE resins with suitable loadings of MSG have remarkably improved integrated performances including mechanical (toughness and rigidity), thermal and dielectric properties. Typically, the MSG/CE resin with 1 wt% MSG shows about 70% higher impact and flexural strengths, 75-15 degrees C enhanced glass transition and initial thermal degradation temperatures as well as lower dielectric loss. Above attractive performances of MSG/CE resins prove that MSG is superior and multi-functional filler, which can simultaneously act as curing catalyst, toughening agent, reinforcement while improving thermal and dielectric properties for heat resistant thermosetting resins. The origin behind attractive results was discussed through intensively investigating the structure of MSG/CE system. (C) 2016 Elsevier B.V. All rights reserved.