A fracture mechanics approach has been used to investigate the effects of the addition of physical modifiers on the fracture energy, G(c), of brittle cyanate-ester polymers. Tests were performed using adhesive joint specimens at -55, 21 and 150degreesC, with all the specimens exhibiting cohesive failure in the cyanate-ester adhesive layer. The fracture energies of systems modified using a range of inorganic and thermoplastic particles, fibres and woven-mats have been measured, and scanning electron microscopy has been used to determine the toughening micromechanisms involved. Firstly, it is shown that the addition of 10% by weight of particulate modifiers can increase the fracture energy of the cyanate-ester polymer by 100%, due to a combination of toughening micromechanisms such as crack deflection, pinning and matrix cavitation around the second-phase particles. These experimental data have been compared to predictions from an analytical model. Secondly, it is demonstrated that the use of long fibres or woven-mats can give an a major increase in the value of the fracture energy, G(c), at initiation, and a further increase with increasing crack length, i.e. a significant 'R-curve' effect is observed. At relatively long crack lengths, the measured fracture energy may be six times greater than that of the unmodified polymer value, due to fibres debonding and bridging across the fracture surfaces. Finally, it is shown that several of the physically-modified polymers developed in the present work have fracture energies that are greater than a typical commercially-available cyanate-ester film adhesive.