With a photoelectron source induced by ultraviolet radiation on mental surface, a photoemission ion mobility spectrometry (PE-IMS) was set up, which can be used to detect halide since halide has a good ability to attach electron. Using CCl4 sample, the evolutions of the ion intensity, full width at half maximum and resolution versus drift electric field, ion gate pulse width and ion gate voltage were obtained, and the reasons for the evolutions were analyzed simply. Taking into account both ion intensity and resolution, optimized experimental parameters were obtained. The PE-IMS has a limit of detection at 4 ppb for CCl4 and its measurable linear dynamics range is over two orders of magnitude in the optimized experimental parameters.