This paper discusses some applications of statistical condition estimation (SCE) to the problem of solving linear systems. Specifically, triangular and bidiagonal matrices are studied in some detail as typical of structured matrices. Such a structure, when properly respected, leads to condition estimates that are much less conservative compared with traditional non‐statistical methods of condition estimation. Some examples of linear systems and Sylvester equations are presented. Vandermonde and Cauchy matrices are also studied as representative of linear systems with large condition numbers that can nonetheless be solved accurately. SCE reflects this. Moreover, SCE when applied to solving very large linear systems by iterative solvers, including conjugate gradient and multigrid methods, performs equally well and various examples are given to illustrate the performance. SCE for solving large linear systems with direct methods, such as methods for semi‐separable structures, are also investigated. In all cases, the advantages of using SCE are manifold: ease of use, efficiency, and reliability. Copyright © 2008 John Wiley & Sons, Ltd.