The three-body Schrödinger equation of the system composed of an α particle He 2+ , a negatively charged pion π − , and an electron interacting through Coulomb forces is solved in perimetric coordinates with the Lagrangemesh method. The ground state, quasibound states, and resonances are obtained for total orbital momenta L = 0 − 20. Mean distances between the particles allow for identifying the structure of these states. The widths of resonances broader than 10 −5 atomic units are derived with the complex scaling method. A transition from atomic to molecular structure occurs between L = 10 and L = 13. Excited levels obtained for L = 0 − 5 display hydrogenlike properties for both the α-pion system and the electron excitations. Excited levels with L 14 correspond to a vibrational excitation of the relative motion of the heavy particles. The validity of the Born-Oppenheimer approximation is found to be fair over the whole range of total orbital momenta.