The Dutchman spent four years at Camp Nou in his playing career but must now try to mastermind a way to defeat the Liga champions in their own back yard.
It will be the first time that the two clubs have met in competitive action and De Boer is wary of the threat that Barcelona pose, particularly with new addition Neymar among their already star-studded ranks.
"I watch almost all of Barcelona's games and I still enjoy watching them on TV because they have so much quality, especially now with Neymar, who is a very special player," he said.
"But they haven't changed that much because almost 90 per cent of the players are still there from last season.
"Neymar is the only change but he's a great player. They are still improving and perhaps some of the players still need to adapt to Neymar.
"But from what I've seen in the last few games, they are improving a lot. There's always a hint of danger for the opposition. Barcelona are a very good side, but I think we all know that."
Despite having never played each other competitively, the two clubs share some common history, with Johan Cruyff the most famous player to have represented both.
He left Ajax to join Barcelona in 1973 and later returned to Amsterdam via a stint in America and a brief spell with Levante.
De Boer feels that Cruyff, who is regarded as one of the most technically gifted players of all time, in many ways sums up the similarities between the clubs.
"Cruyff is a great person and a very important figure for this club and for Barcelona,"he added.
"Both clubs have the same footballing philosophy. Both want to attack and play attractive football with technically strong players. There's not a big difference between the two except for money. The Spanish league is a lot bigger than the Dutch.
"But we are happy with how we are doing with our philosophy, and Barcelona have been employing that same philosophy since (Frank) Rijkaard was in charge."
Rijkaard started and finished his playing career with Ajax and managed Barcelona between 2003 and 2008.
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