The duo made their first appearances in the biennial showpiece back in 1997 when Spanish great Seve Ballesteros captained Europe to victory on home soil.
Playing alongside six time Major Champion and his fellow Englishman Nick Faldo, a young Westwood picked up two points while Dane Bjørn got 1.5 points from a possible two.
More than two decades later, the pair are still going strong and have racked up a combined total of 40 European Tour titles - the most recent of which was Westwood's success at the Abu Dhabi HSBC Championship presented by EGA earlier in the year.
They played together on Saturday at the ISPS HANDA UK Championship at The Belfry last week and they are delighted to be back at the scene of another of their Ryder Cup triumphs this week.
Reminiscing about 1997, Bjørn said: "For me the standout memory of Valderrama is sitting on the driving range for the opening ceremony of the 1997 Ryder Cup.
"The King of Spain was here, Seve being Captain and being part of that team will always be the standout memory for me.
"It was the start of an amazing relationship for me and The Ryder Cup. Being part of that team alongside all of the heroes I grew up with, that for me was such a special moment.
"It doesn’t come much better than Valderrama, it really doesn’t. It tests your game in the right places, your precision, but also your mental attitude toward the game very much.
"It’s just a brilliant golf course to play, one of those great examples of – where every golf course is going for length – that is the last thing that is going to help you here.
"I played a few holes and Valderrama has always been an end of the year tournament coming into October/November time, when it’s softer.
"When you come in the summer it’s a little bit firmer and more tricky. These greens are so small so when they get a bounce in them it’s extremely difficult to keep the ball on the green. It’s a different prospect this week."
Westwood has a decent record at this week's host venue, having finished second at the 2000 WGC-American Express Championship as well as enjoying success at the Ryder Cup.
"I've played well here in the past," he said. "I finished fifth a couple of years ago and I finished second in a World Golf Championships event in 2000 that was round here and I played well at the Ryder Cup...
"Obviously with Seve being captain in his home country, it was great for him and great for European golf.
"And it's always nice to be on a winning Ryder Cup side.
"I grew up watching Seve and Nick (Faldo) and those guys winning tournaments in the 80s and the early 90s.
"So to actually be playing with a hero and be captained by one of your heroes obviously made it a very special week.
"You've got a certain amount of confidence when you look across the tee and you've got Nick Faldo as your partner. You know that he's not going to hit any wide ones and be out of holes so it just allowed me to be aggressive all week."