Charles Leclerc will start a grand prix from pole position for the first time this year with Max Verstappen also on the front row.
Ferrari broke Red Bull's stranglehold on qualifying for the season with Leclerc's stunning lap to secure deny Verstappen.
Saturday's Sprint winner Sergio Perez will start from third with Carlos Sainz completing the top four.
Mercedes has struggled for pace this term, with these difficulties continuing in Azerbaijan despite Lewis Hamilton's respectable fifth-place qualifying.
However, in P11, George Russell highlighted the team's problems.
Alpine has endured a torrid weekend and this continued on Saturday as Esteban Ocon broke parc fermé conditions, resulting in a forced pitlane start.
The Frenchman will be joined in the pitlane by Nico Hulkenberg, who changed his set up following some severe tyre struggles during the Sprint.