We have developed a time-of-flight X-ray photoelectron spectrometer (TOF-XPS) using short pulse X-ray, computer simulations of electron optics and X-ray mirror processing techniques. As a short pulse X-ray source, we adopted a characteristic plasma X-ray which radiates from a target by focused high-power short pulsed laser. For the TOF-XPS system, we adopted a magnetic-bottle method to collect the photoelectrons with high efficiency and high energy resolution. Along to this method, electron optics of the TOF-XPS system was realized by computer simulation techniques. And soft X-ray multilayered mirror with the high-precise surface roughness was produced for high focusing. Using the TOF-XPS system combined we measured the XPS spectra of silicon, gold and tungsten samples and confirmed characteristic peaks of these photoelectron spectra. We succeeded in measuring a chemical shift between tungsten and tungsten oxide at 4 f5/2 and 4 f7/2 peaks. The TOF-XPS system has achieved 0.5 μm spatial resolution with a Schwarzschild X-ray mirror for high spatial resolution.