In this study, the effects of preloaded uniaxial compressive stress and defect (prefabricated by laser cutting) curvature on blast-induced cracks and stress wave propagation were investigated in polymethyl methacrylate (PMMA) specimens using caustics theory. Based on the mathematical relationship between stress and optics, the fracture behavior (the propagation path, dynamic stress intensity factors (DSIFs), propagation velocity, initiation angle of the main crack, and damage degree between the defect and the blasthole) was calculated and analyzed quantitatively. The results show that the preloaded stress could mainly restrain the main crack propagation in the horizontal direction and reduce the initiation angle and damage degree at the defects. Meanwhile, the crack initiation position of the positive curvature defect was not at the end of the defect. In addition, the curvature of the defect significantly affected the blast-induced fracture compared to preloaded stresses. Comparing the main crack with other curvature defects, the DSIFs, velocity, crack arrest time, crack length, and horizontal offset distance of the main crack with negative curvature defect were the largest. The variation in the full stress field in the specimen under blasting and preloaded stress was simulated by a numerical model. The results show that the curvature of the defect has a significant effect on tensile waves at the end of defects, and the tensile stress from high to low was C-25, C0, and C25, in that order.