The recent developments of vacuum ultraviolet (VUV) laser and third generation synchrotron radiation sources, together with the introduction of pulsed field ionization (PFI) schemes for photoion-photoelectron detection, have had a profound impact on the field of VUV spectroscopy and chemistry. Owing to the mediation of near-resonant autoionizing states, rovibronic states of ions with negligible Franck-Condon factors for direct photoionization can be examined by VUV-PFI measurements with rotational resolutions. The VUV-PFI spectra thus obtained have provided definitive ionization energies (IEs) for many small molecules. The recent synchrotron-based PFI-photoelectron-photoion coincidence experiments have demonstrated that dissociative photoionization thresholds for a range of molecules can be determined to the same precision as in PFI-photoelectron measurements. Combining appropriate dissociation thresholds and IEs measured in PFI studies, thermochemical data for many neutrals and cations can be determined with unprecedented precision. The further development of two-color excitation-ionization schemes promises to expand the scope of spectroscopic and chemical applications using the photoionization-photoelectron method.