Abstract The complex band structure (CBS), although not directly observable, determines many properties of a material where the periodicity is broken, such at surfaces, interfaces and defects. Furthermore, its knowledge helps in the interpretation of electronic transport calculations and in the study of topological materials. Here we extend the transfer matrix method, often used to compute the complex bands, to electronic structures constructed using an atomic non-orthogonal basis set. We demonstrate that when the overlap matrix is not the identity, the non-orthogonal case, spurious features appear in the analytic continuation of the band structure to the complex plane. The properties of these are studied both numerically and analytically and discussed in the context of existing literature. Finally, a numerical implementation to extract the CBS from periodic calculations carried out with the density functional theory code siesta is presented. This is constructed as a simple post-processing tool, and it is therefore amenable to high-throughput studies of insulators and semiconductors.