I assume that all multiplicative subsets discussed here are disjoint from $\{0\}$.
Let me write $S$ for the maximal multiplicative subset of $R$.
Step 1: I claim that $S^{-1} R$ is a local ring.
Indeed, if not, there would be at least two maximal ideals in the localization, i.e.,
two prime ideals $\mathfrak{p}_1 \neq \mathfrak{p}_2$, each maximal with respect to
being disjoint from $S$. Thus $S$ is contained in both $R \setminus \mathfrak{p}_1$ and $R \setminus \mathfrak{p}_2$, but these are two different sets so at least one of the containments must be proper, contradicting the maximality of $S$.
Step 2: Therefore there is a unique maximal ideal in the localization, which corresponds to a prime ideal $\mathfrak{p}$ of $R$ which is disjoint from $S$. Arguing as above, maximality of $S$ implies $S = R \setminus \mathfrak{p}$.
Remark 1: When $R$ is a domain, the unique maximal multiplicative subset is obviously $R \setminus \{0\}$. In this case it is tempting to construe "maximal multiplicative subset" to mean "multiplicative subset maximal with respect to being properly contained in $R \setminus \{0\}$."
Remark 2: Conversely, the primes $\mathfrak{p}$ such that $R \setminus \mathfrak{p}$ is maximal are precisely the primes which are minimal with respect to containing $\{0\}$. (When $R$ is a domain and the question is reconstrued as above, we want $\mathfrak{p}$ to be minimal with respect to properly containing $\{0\}$.)
Mariano's answer makes this clear as well.