It depends on the PSV installation configuration with respect to your piping and the vessel. Typically, the PSV is located off a high point so as the material boils in the vessel only the vapor is relieved through the PSV. If the PSV for example was located on the liquid piping, then it 'could' relieve only liquid, but with the volumetric flow rate equal to the amount of vapor being generated inside the vessel due to the fire.
You need to look at your installation detail and decide what is going to happen. Normally, for fire relief, even though do you a 'flash' on the liquid, I've seen vapor relief only listed but I stress you need to look at your installation.