Yes, the action is $(A,x) \mapsto Ax$.
Now fix $x_0 \in S^{n-1}$. Verify that the closed subgroup $G = \{A \in O(n) \mid A x_0 = x_0\}$ fixes the hyperplane $(x_0)^{\perp}$ and that it can be identified with $O(n-1)$. For example, if you take $x_0 = (0,\dots,0,1)$ then $G$ consists of the matrices of the form
$$
\begin{bmatrix}
B & 0 \\
0 & 1
\end{bmatrix} \in O(n), \quad B \in O(n-1).
$$
The to see that $f \colon O(n)/G \to S^{n-1}$ is a homeomorphism, observe that it is a continuous bijection since $O(n)$ acts transitively, then use that a continuous bijection from a compact space to a Hausdorff space is a homeomorphism.