A series of substituted polybenzoxazines was synthesized and studied as binders in non-asbestos friction composite materials. The structures of the polybenzoxazines were varied in a systemic fashion by increasing the number and position of pendant alkyl (methyl) groups and was accomplished using the respective aromatic amines during the polymer synthesis step. By investigating the key thermomechanical and tribological characteristics displayed by the composite materials, the underlying structure-properties relationships were deconvoluted. Composite friction materials with higher thermomechanical and wear resistance properties were obtained from polybenzoxazines with relatively high crosslink densities. In contrast, polybenzoxazines with relatively low crosslink densities afforded composite friction materials with an improved coefficient of friction values and specific wear rates.