A novel copolybenzoxazine was prepared from polybenzoxazine precursor containing polysiloxane (PBA-pdms 600) and ferrocene-based benzoxazine monomer (BA-fcma). The structures of the precursor and monomer were confirmed by IR and H-1 NMR. DSC results suggest that the ring-opening temperature of the copolymers can be decreased by introduction of BA-fcma. SEM illustrates that the domain of the self-crosslinked polyBA-fcma is dispersed into the copolymer networks from nano to micro scale with the increase of BA-fcma. TGA shows that the thermal stability of the copolymers is significantly improved compared with that of homopolymers either in nitrogen or air atmosphere. DMA results exhibit that storage modulus (E') of the copolymers is greatly enhanced. The three peaks in tan delta curve illustrate that there are three crosslinking structures in the copolymers. The structure and the degradation mechanism of the copolymers are investigated by Pyrolysis/GC-MS technique. (C) 2013 Elsevier Ltd. All rights reserved.