We provide an overview of the successive steps that made it possible to obtain increasingly accurate excitation energies with computational chemistry tools, eventually leading to chemically accurate vertical transition energies for small- and medium-size molecules. First, we describe the evolution of ab initio methods employed to define benchmark values, with the original Roos CASPT2 method, then the CC3 method as in the renowned Thiel set, and more recently the resurgence of selected configuration interaction methods. The latter method has been able to deliver consistently, for both single and double excitations, highly accurate excitation energies for small molecules, as well as medium-size molecules with compact basis sets. Second, we describe how these high-level methods and the creation of representative benchmark sets of excitation energies have allowed the fair and accurate assessment of the performance of computationally lighter methods. We conclude by discussing possible future theoretical and technological developments in the field.