Not if the RDBMS is a column store. Or if the storage model is based on log-structured merge trees. There are many ways to map the relational model to storage. Even for the traditional row-oriented case in InnoDB there are structures like B+-tree indexes that do not directly correspond to a K:V store.
* A main key/value collection consisting of primary key (key) mapping to a serialization of the row (value)
* One key/value collection per index consisting of each index function applied to the row (key) mapping to the primary key (or some internal object id; the value)
It's a bit of a simplification as an RDBMS needs to maintain a sort-order and allow e.g. range queries, and need interfaces that allow reading/writing lots of rows with low per-row overhead, and so it's not that they'd be a good match for just any key-value store.
That said, I don't think this is the usage scenario most DBMS are optimized for, because despite being common, it's a very fast case, so there is relatively little to gain. At the same time, this is the only usage of k:v storage, so you bet it's optimized for that.