Direct piezoelectric strain energy harvesting can be used to power wireless autonomous sensors in environments where low frequency, high strains are present, such as in automobile tires during operation. However, these high strains place stringent demands on the materials with respect to mechanical failure or depolarization, especially at elevated temperatures. In this work, three kinds of ceramic–polymer composite piezoelectric materials were evaluated and compared against state-of-the-art piezoelectric materials. The new composites are unstructured and structured composites containing granular lead zirconate titanate (PZT) particles or PZT fibers in a polyurethane matrix. The composites were used to build energy harvesting patches which were attached to a tire and tested under simulated rolling conditions. The energy density of the piezoelectric ceramic–polymer composite materials is initially not as high as that of the reference materials (a macro-fiber composite and a polyvinylidene fluoride polymer). However, the area normalized power output of the composites after temperature and strain cycling is comparable to that of the reference devices because the piezoelectric ceramic–polymer composites did not degrade during operation.