Let $A$ be a subcomplex of CW-complex $X$. The excision axiom for homology implies that $H_i(X, A)\cong H_i(X/A, *)$, and it is widely known that homotopy groups don't have this property. However, they satisfy a significantly weaker Blakers-Massey theorem. One of its consequences is that when $A$ is $n$-connected and the inclusion $A\to X$ is an isomorphism on the first $s$ homotopy groups, $\pi_k(X, A) \cong \pi_k(X/A, *)$ for $k < s + n - 1$.
Thus to devise an example where $\pi_k(X, A) \not\cong \pi_k(X/A, *)$ it's necessary to take large enough $k$, and the calculation of both sides becomes hard. The original paper of Blakers and Massey claims there are simple examples, but I wasn't able to make them up myself. What are some simple examples of the pairs $(X, A)$ and $(X/A, *)$ with different homotopy groups? Preferably with both $A$ and $X$ simply connected.
Well, I figured some examples. The easiest is probably $S^2 \hookrightarrow S^3$ as an equator. Here $\pi_4(S^3, S^2) \cong \mathbb{Z}\oplus \mathbb{Z}/2\mathbb{Z}$ by the exact sequence of a pair (the inclusion is obviously null-homotopic, so maps $\pi_k(S^2)\to\pi_k(S^3)$ are all zero). On the other hand, the quotient is a wedge of two three-spheres, and $\pi_4(S^3 \vee S^3)$ is equal to $\pi_4(S^3 \times S^3) = \mathbb{Z}/2\mathbb{Z} \times \mathbb{Z}/2\mathbb{Z}$ since $\pi_4$ depends only on 5-skeleton, while $S^3 \times S^3$ is $S^3\vee S^3$ with a 6-cell attached.
It is also true for $S^1\hookrightarrow S^2$, though you need more machinery. $\pi_3(S^2, S^1)$ is $\mathbb{Z}^2$ by the exact sequence of a pair as well. On the other hand, $\pi_3(S^2 \vee S^2) \cong \mathbb{Z}^3$ using the standard trick: fiber of $S^2 \vee S^2 \to K(\mathbb{Z}, 2)\times K(\mathbb{Z}, 2)$ has $H^3 \cong \mathbb{Z}^3$ by Serre's spectral sequence.