Fracture toughness measures the resistance of a material to fracture. This fundamental property is used in diverse engineering designs including mechanical, civil, materials, electronics and chemical engineering applications. In spite of the advancements made in the past 40 years, the evaluation of this remains challenging for extremely heterogeneous materials such as composite concretes. By taking advantage of the optical properties of a thin birefringent coating on the surface of opaque, notched composite concrete beams, here we sense the evolution of the maximum shear stress distribution on the beams under loading. The location of the maximum deviator stress is tracked ahead of the crack tip on the experimental concrete samples under the ultimate load, and hence the effective crack length is characterised. Using this, the fracture toughness of a number of heterogeneous composite beams is evaluated and the results compare favourably well with other conventional methods using combined experimental and numerical/analytical approaches. Finally a new model, correlating the optically measured shear stress concentration factor and flexural strength with the fracture toughness of concretes is proposed. The current photonics-based study could be vital in evaluating the fracture toughness of even opaque and complex heterogeneous materials more effectively in future.