The Dutchman left Camp Nou in 2008 and has since seen Pep Guardiola revolutionise the club - winning 14 titles in four seasons - while Tito Vilanova has overseen Barca's best ever start to a league season in the current campaign.
And Rijkaard, who is currently Saudi Arabia head coach, believes that organisation is crucial when you play against the Catalan club, but believes that Jose Mourinho's method will not always pay off.
"There’s no magic bullet, but you have to adapt to their style," the Dutchman told Fifa.com.
"Most of the clubs who have had success against Barcelona have relied on a highly organised and disciplined defence.
"Inter and Chelsea have both sent Barcelona out of the Champions League and then you have Real Madrid [who won La Liga in 2011-12].
"You could call it the 'Jose Mourinho recipe for success', which he began while he was at Chelsea. If you play Barcelona that way 10 times, you might beat them once, but it certainly doesn't guarantee success."
When asked who he thinks will win the upcoming Ballon d’Or - which is between Cristiano Ronaldo, Lionel Messi and Andres Iniesta - Rijkaard rooted for the Argentine forward, who he hailed as "exceptional".
"I'm going for Lionel Messi, because I think he's the best player on the three-man final shortlist and he's performed brilliantly this year," the ex-Ajax star continued.
"He's an incredible person. Messi is not simply a uniquely talented footballer. He's also strong mentally, very bright and exceptionally dedicated to his job.
"Personally speaking I enjoy watching him play and I'm deeply proud of him and what he has achieved. Quite simply, he's the best."