There are infinitely many configurations of a vector field $A_\mu$ that describe the same physical situation. This is a result of our gauge freedom $$ A_\mu (x_\mu) \to A'_\mu \equiv A_\mu (x_\mu) + \partial_\mu \eta(x_\mu ),$$ where $\eta (x_\mu)$ is an arbitrary scalar function.
Therefore, each physical situation can be described by an equivalence class of configurations. All members within a given equivalence class are related by a gauge transformation. Configurations in different equivalence classes describe physically distinct situations and therefore are not related by gauge transformations.
To fix the gauge, we need to pick exactly one member from each such equivalence class. A popular way to accomplish this is by demanding \begin{equation} \partial_i A_i =0 \, . \end{equation} Apparently this works because there is only exactly one member in each equivalence class that fulfills this additional condition. How can this be shown and understood?
PS: I asked a very similar question recently, but made a typo in the gauge condition (Lorenz gauge instead of Coulomb gauge). The Lorenz gauge condition, of course, leaves a residual gauge freedom, while the Coulomb gauge is a physical gauge.