Straight from kick-off, the visitors were pinned back with Lee Mathews firing a warning shot over the bar in only the third minute.
A goal didn't take long in coming and it arrived in style when, after 16 minutes, Vale Park was treated to one of the goals of the season.
Christopher Birchall's storming run upfield and one-two with Mathews resulted in a blazing half-volley into Scott Flinders' top corner.
Barnsley's best and only real chance of the half fell to Nathan Jarman but his close-range shot was blocked by Mark Goodlad.
Billy Paynter emulated his team-mate four minutes before the break when he thumped a shot from the same spot and into the same place.
Then only five minutes after the restart he went one better when he rolled Michael Cummins' through ball underneath Flinders from 12 yards.
On-loan Tony Dinning was the next to step up and compound Barnsley's misery when he nodded home a cross from Cummins.
The midfielder didn't stop there and after Nathan Lowndes was fouled on the edge of the area, he hammered the set-piece soundly into Flinders' top left-hand corner.
The Tykes never really threatened but Goodlad was called into action 15 minutes from the end with a superb finger-tip save from a Chris Shuker 10-yard shot.