The game exploded into life when Cristian Villagra was sent off after conceding a penalty 25 minutes in.
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Balazs Dzsudzsak converted from the spot and, while Metalist were still reeling, Marcus Berg pounced two minutes later to make it 2-0.
That ultimately proved enough for PSV to displace their opponents as group leaders on four points, level with Sampdoria.
Metalist had romped to a 5-0 victory in their Group I opener at Debrecen but they were unable to dominate from the off tonight, with Berg seeing an early header blocked by Papa Gueye.
Freda Taison sent Metalist's first effort off target from 12 yards in the 19th minute before the entire contest was thrown wide open by Villagra's red card.
Dzsudzsak's 28th-minute penalty rubbed salt into the wound and Berg capitalised on the disarray on the half-hour mark when he fired home left-footed from 12 yards.
Vinicius Fininho tried to respond for Metalist but saw his 18-yard shot blocked by Ibrahim Afellay and it almost got worse for the 10 men when Ola Toivonen clattered the crossbar from outside the box.
Dzsudzsak was off target from the edge of the area shortly before the hour mark and Jeremain Lens should have killed the tie when he headed wide from six yards in the 65th minute.
But PSV were almost entirely untroubled for the rest of the evening, with Metalist's only significant attempt in the final half-hour coming 11 minutes from time when Fininho dragged his finish wide from 12 yards.
The defeat saw Metalist slide to third in Group I, though they are only one point behind PSV and Samp.
Source: DSG
