The Silver Arrow machine has now been on pole in Berlin, Diriyah, Rome and Valencia - the most recent four events - with Vandoorne leading the way in Spain by three hundredths of a second.
Vandoorne, winner of Rome race two, progressed through from the opening group run to book his place in the top-six superpole shootout where he set a 1m26.494s effort.
His run looked scruffy and he was marginally up against the benchmark of reigning champion Antonio Felix da Costa in the second sector.
But Vandoorne, who clipped the wall on his preparation lap, delivered superbly through the final section of the Circuit Ricardo Tormo to secure his fourth Formula E pole position.
Da Costa was knocked to the outside of the front row of the grid, having held on strongly from running second in superpole,