Recently, hot stamping technology has been increasingly used in automotive structural parts with ultrahigh strength to meet the standards of both high fuel efficiency and crashworthiness. However, one issue of concern regarding these martensitic steels, which are fabricated using a hot stamping procedure, is that the steel is highly vulnerable to hydrogen delayed cracking caused by the diffusible hydrogen flow through the surface reaction of the coating in a furnace atmosphere. One way to make progress in understanding hydrogen delayed fractures is to elucidate an interaction for desorption with diffusible hydrogen behavior. The role of diffusible hydrogen on delayed fractures was studied for different baking times and temperatures in a range of automotive processes for hot-stamped martensitic steel with aluminum- and silicon-coated surfaces. It was clear that the release of diffusible hydrogen is effective at higher temperatures and longer times, making the steel less susceptible to hydrogen delayed fractures. Using thermal desorption spectroscopy, the phenomenon of the hydrogen delayed fracture was attributed to reversible hydrogen in microstructure sites with low trapping energy.