Nico Rosberg became the first driver this year to beat Lewis Hamilton on a Saturday afternoon when he took a comfortable pole position in Spain.
Rosberg took the early advantage in Q3 as he crossed the line after Hamilton with a 1:24.681. That gave him a 0.267s advantage over his team-mate ahead of their final run.
That run, though, saw none of the top five able to improve their lap times despite a few personal best sectors.
As such, Rosberg claimed pole position, his first of this season, ahead of Hamilton.
Vettel qualified his Ferrari in third place, 0.777s down on the Mercedes pole-sitter.
Rosberg, Hamilton and Vettel all used the hard tyres to make it through the first segment of qualifying which means the trio will head into Sunday's 66-lap Spanish GP with an extra set of the option tyres available.
Valtteri Bottas was fourth quickest while Carlos Sainz got the Spanish crowd up on their feet as he brought his STR home in fifth place ahead of Max Verstappen.
Kimi Raikkonen dropped to seventh place ahead of Danill Kvyat, Felipe Massa and Daniel Ricciardo.
For the first time this season both McLarens made it through to Q2. But that's where it ended.
Fernando Alonso qualified P13 and Jenson Button P14 with both drivers over eight-tenths away from a place in the pole position shoot-out.
Meanwhile, it was a dismal Saturday for Force India. Waiting on the introduction of a B-spec car, Nico Hulkenberg and Sergio Perez were a disappointing 17th and 18th with only the Manor drivers slower.
1 Nico Rosberg Mercedes 1:24.681
2 Lewis Hamilton Mercedes 1:24.948 0.267
3 Sebastian Vettel Ferrari 1:25.458 0.777
4 Valtteri Bottas Williams 1:25.694 1.013
5 Carlos Sainz Toro Rosso 1:26.136 1.455
6 Max Verstappen Toro Rosso 1:26.249 1.568
7 Kimi Raikkonen Ferrari 1:26.414 1.733
8 Daniil Kvyat Red Bull 1:26.629 1.948
9 Felipe Massa Williams 1:26.757 2.076
10 Daniel Ricciardo Red Bull 1:26.770 2.089
11 Romain Grosjean Lotus 1:27.375
12 Pastor Maldonado Lotus 1:27.450
13 Fernando Alonso McLaren 1:27.760
14 Jenson Button McLaren 1:27.854
15 Felipe Nasr Sauber 1:28.005
16 Marcus Ericsson Sauber 1:28.112
17 Nico Hulkenberg Force India 1:28.365
18 Sergio Perez Force India 1:28.442
19 Will Stevens Manor 1:31.200
20 Roberto Merhi Manor1:32.038