This research proposed a novel nano barium strontium titanate (BST) powder- polybenzoxazine composite as a new dielectric material. In this work, the dielectric properties of a surface-treated BST powder-polybenzoxazine composite were studied. The surface of the BST powders were modified by using three different chemicals: 3-aminopropyl-trimethoxysilane, benzoxazine monomer and phthalocyanine. The distribution of the BST powders in the polybenzoxazine matrix was observed by SEM. The dielectric constants of the composites with a function of frequency (1 kHz–10 MHz) were investigated. It was found that the composites with modified BST powders showed good distribution in the polybenzoxazine matrix, and the dielectric constants were also much enhanced than those with untreated BST powders. In comparisons among the three modification methods, the composite with the silane coupling modified BST powder showed significantly in dielectric constant improvement while the composite with the benzoxazine and phthalocyanine modified BST powders displayed lower dielectric loss due to the modified powder dispersed well in the polybenzoxazine matrix.