In this work, the two-center Dirac equation is solved numerically using an extension of an adapted B-spline basis set method previously implemented in relativistic atomic calculations (Fischer, C. F.; Zatsarinny, O. Comput. Phys. Commun. 2009, 180, 879). The robustness of the chosen numerical method, which avoids the appearance of spurious states common in other approaches, allows us to investigate molecular photoionization within a relativistic framework by simply adapting those methods already available in the nonrelativistic case (