An important property of the derived category is that distinguished triangles don't just produce long exact sequences in cohomology. If A -> B -> C -> A[1] is an exact triangle and E is another object in the derived category, then you get a long exact sequence
... Hom(A[1],E) -> Hom(C,E) -> Hom(B,E) -> Hom(A,E) -> Hom(C[-1],E) -> ...
where these Hom-sets are sets of maps in the derived category.
A particular counterexample is as follows. We can view any abelian group as a chain complex concentrated in degree zero. There is a distinguished triangle as follows:
ℤ -> ℤ -> ℤ/2 -> ℤ[1]
However, we can take the last map ℤ/2 -> ℤ[1] in the sequence (which is not zero in the derived category) and replace it with the zero map. This still gives us a long exact sequence on (co)homology groups. However, if we let E = ℤ/2, then applying maps in the derived category from our new non-distinguished triangle gives us the sequence
... 0 -> Hom(ℤ/2,ℤ) -> Hom(ℤ,ℤ) -> Hom(ℤ,ℤ) -> Ext(ℤ/2,ℤ) -> 0 ...
where the last map is induced by the zero map from ℤ/2[-1] to ℤ, and so it must be zero. This sequence can't possibly be exact, and so the new triangle is not distinguished.
EDIT: A more subtle question this suggests is: "Suppose I have a triangle and, for any E, applying Map(-,E) or Map(E,-) gives a long exact sequence. Is this a distinguished triangle?"
The answer to this is actually still no. Still considering chain complexes of abelian groups, take the distinguished triangle
ℤ -> ℤ -> ℤ/3 -> ℤ[1]
where I'll call the last map β (for Bockstein). You can take this distinguished triangle and replace β with its negative -β. The new triangle still induces long exact sequences on maps in or maps out (because the maps in the triangle have the same kernel and image). However, as an exercise show that this can't be a disntinguished triangle because it's not isomorphic to the original distinguished triangle.