SummaryTwo classes of methods for approximate matrix inversion with convergence orders p=3∗2k+1 (Class 1) and p=5∗2k−1 (Class 2), k≥1 an integer, are given based on matrix multiplication and matrix addition. These methods perform less number of matrix multiplications compared to the known hyperpower method or pth‐order method for the same orders and can be used to construct approximate inverse preconditioners for solving linear systems. Convergence, error, and stability analyses of the proposed classes of methods are provided. Theoretical results are justified with numerical results obtained by using the proposed methods of orders p=7,13 from Class 1 and the methods with orders p=9,19 from Class 2 to obtain polynomial preconditioners for preconditioning the biconjugate gradient (BICG) method for solving well‐ and ill‐posed problems. From the literature, methods with orders p=8,16 belonging to a family developed by the effective representation of the pth‐order method for orders p=2k, k is integer k≥1, and other recently given high‐order convergent methods of orders p=6,7,8,12 for approximate matrix inversion are also used to construct polynomial preconditioners for preconditioning the BICG method to solve the considered problems. Numerical comparisons are given to show the applicability, stability, and computational complexity of the proposed methods by paying attention to the asymptotic convergence rates. It is shown that the BICG method converges very quickly when applied to solve the preconditioned system. Therefore, the cost of constructing these preconditioners is amortized if the preconditioner is to be reused over several systems of same coefficient matrix with different right sides.