The temporal profile and phase of the fifth harmonic of a Ti:sapphire laser were fully characterized by two-photon ionization frequency-resolved optical gating technique for the first time. The fifth harmonic was found to have negative chirp and the pulse compression was demonstrated. The negative chirp is well explained by using a zero-range potential model. This technique is scalable to extreme ultraviolet (XUV) and soft x-ray regions by using currently available light sources, making it possible to measure the pulse duration and phase of vacuum ultraviolet, XUV, and soft x-ray pulses.