AbstractWe determine the asymptotics of the block Toeplitz determinants as for matrix‐valued piecewise continuous functions with a finitely many jumps under mild additional conditions. In particular, we prove that where , , and are constants that depend on the matrix symbol and are described in our main results. Our approach is based on a new localization theorem for Toeplitz determinants, a new method of computing the Fredholm index of Toeplitz operators with piecewise continuous matrix‐valued symbols, and other operator theoretic methods. As an application of our results, we consider piecewise continuous symbols that arise in the study of entanglement entropy in quantum spin chain models.