The influence of the spectrum of original and preconditioned matrices on a convergence rate of iterative methods for solving systems of finite-difference equations applicable to two-dimensional elliptic equations with mixed derivatives is investigated. It is shown that the efficiency of the bi-conjugate gradient iterative methods for systems with asymmetric matrices significantly depends not only on the matrix spectrum boundaries, but also on the heterogeneity of the distribution of the spectrum components, as well as on the magnitude of the imaginary part of complex eigenvalues. For test matrices with a fixed condition number, three variants of the spectral distribution were studied and the dependences of the number of iterations on the dimension of matrices were estimated. It is shown that the non-uniformity in the eigenvalue distribution within the fixed spectrum boundaries leads to a significant increase in the number of iterations with increasing dimension of the matrices. The increasing imaginary part of the eigenvalues has a similar effect on the convergence rate. Using as an example the model potential distribution problem in a square domain, including anisotropic ring inhomogeneity, a comparative analysis of the matrix structure and the convergence rate of the bi-conjugate gradient method with Fourier – Jacobi and incomplete LU factorization preconditioners is performed. It is shown that the advantages of the Fourier – Jacobi preconditioner are associated with a more uniform distribution of the spectrum of the preconditioned matrix along the real axis and a better suppression of the imaginary part of the spectrum compared to the preconditioner based on the incomplete LU factorization.