Cramer's Rule is a method for solving systems of linear equations using determinants. It can be used to solve systems with the same number of equations as unknowns. The rule involves writing the system as a coefficient matrix and calculating determinants of the matrix and related matrices to find the values of the unknowns. If the determinant of the coefficient matrix is zero, the system has no unique solution or an infinite number of solutions. Otherwise, Cramer's Rule provides a way to calculate the specific values of each unknown.