Defending champions Feyenoord lost their first game of the season, while title rivals Ajax also dropped points in Sunday’s Eredivisie action.
PSV moved level with Feyenoord at the league summit courtesy of their narrow 1-0 victory at the Philips Stadion, where Gaston Pereiro’s second-minute goal settled matters.
De Stadionclub lost their 100% record in the league as De Boeren moved into a three-way tie at the top of the table on 12 points.
Elsewhere, Twente picked up their first win of the new campaign with a 4-0 thrashing of Utrecht at De Grolsch Veste.
The Tukkers came into the match having lost their opening four encounters, but they got off to a flying start when Tom Boere opened the scoring in the ninth minute before Thomas Lam doubled their advantage nine minutes later.
Further goals from Luciano Slagveer (35′) and Ousama Assaidi (75′) saw Rene Hake’s side halt a four-match losing streak, although it was not enough to lift them out of the relegation zone in 16th place.
Meanwhile, Ajax were denied a fourth straight win after being held to a 1-1 draw by ADO Den Haag at the Cars Jeans Stadion.
Marcel Keizer’s men took a 1-0 lead into the break thanks to Joel Veltman’s 28th-minute opener, but the hosts hit back in the second half through Bjorn Johnsen (71′) to earn a share of the spoils.
The Amsterdam giants are two points off the pace in sixth spot, while the Hague find themselves just one point clear of the bottom three in 14th position.
Newly-promoted VVV needed a last-gasp equaliser to clinch a 1-1 draw with Vitesse at the GelreDome, which left them mid-table after five rounds.
After a goalless first half, Tim Matavz put the hosts ahead just two minutes after the restart, but they were denied back-to-back wins as Clint Leemans restored parity from the penalty spot at the death.
The Venlo outfit occupy ninth spot, just two points adrift of Vitas in fifth place.
Sunday’s Eredivisie results:
ADO Den Haag 1-1 Ajax
Twente 4-0 Utrecht
Vitesse 1-1 VVV
PSV 1-0 Feyenoord