Using a penetration-field threshold photoelectron (TPE) analyzer and efficient photon detectors X-ray-emission-threshold-electron coincidence (XETECO) spectroscopy has been developed to a point where peak shape analysis becomes meaningful. The spectra can, on the present level of accuracy, be interpreted as conventional TPE spectra free from post collision interaction effects. For the neon atom and the nitrogen molecule we find a detailed correspondence with state-of-the-art photoemission spectra, both regarding peak positions, line shapes, and relative intensities. Intensity redistribution due to fast core vacancy rearrangement processes in systems with close-lying core levels, like O-2, N2O, and NO is briefly discussed. It is demonstrated that even the complex threshold behavior at the F K threshold in SF6 leads to a well-defined XETECO peak, directly corresponding to classical photoemission results. (C) 2004 Elsevier B.V. All rights reserved. (Less)