Background
It is known that there exists an oracle $A$ such that, $PSPACE^A \neq PH^A$.
It is even known that the separation holds relative to a random oracle. Informally, one may interpret this to mean that there are many oracles for which $PSPACE$ and $PH$ are separate.
Question
How complicated are these oracles that separate $PSPACE$ from $PH$. In particular, is there an oracle $A \in DTIME(2^{2^{n}})$ such that $PSPACE^A \neq PH^A$?
Do we have any oracle $A$ such that $PSPACE^A \neq PH^A$ and $A$ has a known complexity upper bound?
Note: the existence of such an oracle may have ramifications in structural complexity theory. See the following update below for further details.
Update with details on a lower bound technique
Claim: If $PSPACE = PH$, then for all oracles $A \in P/poly$, $PSPACE^A = PH^A$.
Proof Sketch: Suppose that $PSPACE = PH$.
Let an oracle $A \in P/poly$ be given. We can build a polynomial time $\Sigma_2$ oracle Turing machine $M$ that for a given length $n$, guesses a circuit of size $p(n)$ using an existential quantification and verifies that the circuit decides $A$ by comparing the evaluation of the circuit and the query result for every length $n$ string using a universal quantification.
Further, consider a decision problem that I'm referring to as quantified Boolean circuit (QBC) where you are given a quantified boolean circuit and want to know if it valid (similar to QBF). This problem is PSPACE-complete because QBF is PSPACE-complete.
By assumption, it follows that QBC $\in PH$. Let's say $QBC \in \Sigma_k$ for some $k$ sufficiently large. Let $N$ denote a polynomial time $\Sigma_k$ Turing machine that solves QBC.
We can intermingle the computation of $M$ and $N$ (similar to what is done in the proof of the Karp-Lipton theorem) to get a polynomial time $\Sigma_k$ oracle Turing machine that solves $QBC^A$.
Informally, this new machine takes as input an oracle QBC (that is a QBC with oracle gates). Then, it computes a circuit that computes $A$ on inputs of length $n$ (simultaneously pealing off the first two quantifiers). Next, it replaces the oracle gates in the oracle QBC with the circuit for $A$. Finally, it proceeds to apply the remainder of the polynomial time $\Sigma_k$ algorithm for solving $QBC$ on this modified instance.
Now, we can show the conditional lower bound.
Corollary: If there exists an oracle $A \in NEXP$ such that $PSPACE^A \neq PH^A$, then $NEXP \nsubseteq P/poly$.
Proof Sketch: Suppose that there exists $A \in NEXP$ such that $PSPACE^A \neq PH^A$. If $NEXP \subseteq P/poly$, then we would get a contradiction.
In particular, if $NEXP \subseteq P/poly$, then by the claim above we have $PSPACE \neq PH$. However, it is known that $NEXP \subseteq P/poly$ implies that $PSPACE = PH$.
(see here for some details on known results for P/poly)