Sykes put in a sensational 1'38.592 while threading his way past the touring Eugene Laverty, Vincent Philippe and Chaz Davies at the back of the circuit, and he was 1.3s ahead before Aprilia's Guintoli pulled back the gap.
Davide Guigliano put in a lap in the middle of the session, which had been declared wet but run on a dry track, which was enough to ward off the attentions of Laverty and keep him off the front row.
Michel Fabrizio, on the sister Pata Honda to Leon Haslam, joins Laverty on row two with Alstare Ducati's Ayrton Badovini in sixth. Marco Melandri, Chaz Davies and Philippe round out the finishers.
1. Sykes (Kawasaki) 1'38.592
2. Guintoli (Aprilia) 1'39.397
3. Giugliano (Aprilia) 1'39.933
4. Laverty (Aprilia) 1'40.410
5. Fabrizio (Honda) 1'40.864
6. Badovini (Ducati) 1'40.926
7. Melandri (BMW) 1'41.361
8. Davies (BMW) 1'41.375
9. Philippe (Suzuki) 1'47.691