Benzoxazine resins (BZs) as a novel type of phenolic resin are high-performance matrix resin for advanced composites. Yet there still exist some deficiencies when used as ablative material in aerospace applications, such as high curing temperature and poor thermal stability. In the present study, the phenylboronic add (PEA) modified BZs (PBBZs) exhibiting excellent processibilities and thermal properties were prepared by incorporating PBA into BZ. The viscosity, gel time and curing behaviors were examined to demonstrate that PBBZs possessed better processibilities than the BZ, representing the catalytic effect of PBA in this case. The incorporation of PBA accelerated the ring-opening polymerization of BZ, leading to the lower curing temperature. TGA results reveal that the cured PBBZs exhibit excellent thermal properties, where the char yield at 800 degrees C (nitrogen atmosphere) reaches 63.7% and is increased by 14.1 percentage points than that of BZ. The formed phenylboronates during curing act as additional cross-linking points and increase the cross-linking density of the cured resin, which results in the enhancement of the glass transition temperature of BZ ranging from 165 degrees C to 219 degrees C. This study provides a new vision for the preparation of high-performance matrix resin for ablative materials by introducing aryl-boron backbone. (C) 2015 Elsevier B.V. All rights reserved.