Without being able to prove in ZFC that the unordered pair $\{x,y\}$ exists whenever $x, y$ are sets, all you have is a notation, $\{x,y\}$, for that unique set which, if it exists, contains just $x$ and $y$. The notion that "a set exist[s] simply by virtue of the fact that it has a definition" is codified by the (false, inconsistent) "naive Comprehension" principle, which claims that for any formula $\psi(x)$, the collection $\{x\,|\,\psi(x)\}$ is a set. Taking $\psi(x)$ to be $x\notin x$ gives the Russell paradox.
Pairing is redundant in the presence of other axioms. Given the Axiom of Infinity (in its usual formulation) and Separation, you can show that the set $2 = \{\emptyset, \{\emptyset\}\} = \{0, 1\}$ exists. Similarly, If you have existence of $\emptyset$ and the Powerset axiom, again $2 = \mathcal{P}(\mathcal{P}(\emptyset))$ is provably a set.
Now, given any sets $a, b$, the class function $F$ given by $0 \mapsto a, 1 \mapsto b$ is definable — for example, by this formula with parameters $a, b$:
$$\varphi(x, y) =_{def} (x=0\land y=a)\lor(x=1\land y=b).$$
Because $2$ as above is a set, by Replacement its image under $F$ is a set. That image is $F[2] = \{y\,|\, (\exists x\in 2)\, \varphi(x, y)\} = \{a, b\}$.
Pairing exists as a separate axiom because we want to be able to study the systems that result from dropping other ZFC axioms such as Infinity, Replacement, or Powerset. The remaining core of axioms should characterize basic aspects of "sethood" that don't involve those notions. Pairing is a basic requirement we have for universes of sets — whatever else a model of set theory does or doesn't contain, surely it ought to be closed under pairing.
Note that Separation can be proved from Replacement and the other ZFC axioms, but it's retained in most presentations as a separate axiom schema, for pedagogical reasons — it provides an opportunity to discuss naive Comprehension and the resulting inconsistencies — and because ZC, ZFC minus Replacement, came first and remains a thing.