A laser-based instrument is described for the study of femtosecond dissociation dynamics of gas phase molecules via time-resolved vacuum ultraviolet and soft x-ray photoelectron spectroscopy. Visible or UV pump pulses are generated with nonlinear crystal techniques on a Ti:sapphire laser output, while soft x-ray probe pulses are created via high-order harmonic generation of the same laser in rare gases. Here we describe the optical layout of the pump-probe system, the means for separation of the high-order harmonics in the soft x-ray probe beam, including a description of the two grating setup used to compress the high-harmonic pulses and the magnetic bottle photoelectron spectrometer used for data collection. The feasibility of using the generated high-harmonic pulses for an array of gaseous phase photoelectron spectroscopy experiments is established. These include measurements of valence shell and core-level photoelectron transitions in atoms and molecules, the tunability of the soft x-ray harmonic through Rydberg resonances, and the energy bandwidths of the harmonics. Cross correlations between the visible/UV and soft x-ray pulses, by above threshold ionization, are used to establish the pulse timing, pulse duration, and spatial overlap for ultrafast studies. The observed real time photodissociation of Br2 serves as a demonstration of the pump-probe ultrafast technique and the applicability to ultrafast time-resolved chemical dynamics.