This study demonstrates hydrogen production from seawater electrolysis via protonic ceramic electrochemical cells (PCECs) for the first time. Using vapors generated from seawater, a state-of-the-art air electrode PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) shows a typical area-specific resistance of 0.269 Ω cm2 with reasonable durability within a 100 h test at 600 °C, similar to those tests using pure water vapor. In addition, in seawater vapor at 600 °C, a PCEC with a cell configuration of PBSCF∣BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb)∣Ni-BZCYYb shows a typical peak power density of 1.388 W cm−2 in a fuel cell (FC) mode and a current density of −2.392 A cm−2 in an electrolysis cell (EC) mode. In addition, the cells show promising stability in seawater vapor (3% and 10% H2O concentration) in EC mode when tested at −0.5 A cm−2 at 600 °C. More importantly, the cells maintain a reliable hydrogen production rate and faradaic efficiency during the seawater electrolysis.