The Spaniard was in charge at Camp Nou when the Blaugrana made their ascent to the best team in Europe, winning the Champions League twice in three years.
On Wednesday, the Bundesliga giants revealed Guardiola had signed a three-year deal with the Bavarians, beginning at the end of the current season, but De Boer believes he will struggle to replicate his trophy haul at Barca even if he does succeed at his new club.
"Of course he had good players at Barcelona, but he showed us the 'hand of Guardiola,'" the former team-mate to the incoming Allianz Arena coach told BBC Sport. "I am 100 per cent convinced of it.
"I think he will do the same at Bayern. You can never know for sure if he will succeed and I don't know if he will win as much as he did with Barcelona, but you can already see that there will be a Guardiola team playing to win the Champions League next season."
De Boer believes the way Bayern are organised helped the German club beat the nouveau-riche of Europe to the coach’s signature, and hailed the Bundesliga as one of the best leagues on the planet.
"I think it will be down to the structure of the club,” the former Netherlands international added.
"I still speak to former Bayern coach Louis van Gaal and he always says it is a very professional club, a well-run club, with the same kind of philosophy as Barcelona. So they will understand what Pep will be trying to do.
"As far as the Bundesliga goes, it is a very interesting league and definitely on the up. Maybe it is passing La Liga, and it passed Serie A a long time ago.
"I think because of the crowds they get, it is up with the Premier League. The atmosphere in the stadiums is best in England, but in Germany it is similar."
De Boer, whose Ajax youth academy is one of the most admired in Europe, believes Jupp Heynckes’ replacement could help turn the Bavarians’ prospects into first-team stars.
“There is a youth programme there, which is okay, but I think Bayern can still build on it," the Eredivisie coach added.
"If you look at the kind of players who have come from their youth teams and who are playing in their first team, then, I think they can do more with their programme.
"But we don't know yet what their plans are for the academy or what plans they have got for Pep. He might be overseeing that as well or he might be only concerned with the first team. We will have to wait and see."
Barcelona are famous for playing with flair and having a focus on possession football in the modern game, which Guardiola helped to forge, but De Boer thinks the coach is adaptable and will not necessarily change how the Bavarians play their game.
He said: "He might adapt it but it will not change much. I know him well and he is a smart guy so he will always look at what kind of players he has, and from there he will get the best concept to play."