Yes. Since $I$ is non-singular, we may define in its small neighbourhood a matrix logarithm. It follows that $f(t) = \log U(t)$ is well defined in some neighbourhood of zero because $U$ is continuous and $U(0)=I$.
By definition, the subgroup $\{U(t): t\in\mathbb R\}$ is Abelian. Hence $\log\left(U(s)U(t)\right)=\log U(s)+\log U(t)$. Consequently, if we denote by $f_{ij}$ the $(i,j)$-th component of $f$, then we can reduce the original functional equation to
$$
f(s+t)=f(s)+f(t)
$$
or $f_{ij}(s+t)=f_{ij}(s)+f_{ij}(t)$ for each $(i,j)$. This is basically Cauchy's functional equation, with the exception that the domain of $f_{ij}$ is a neighbourhood of zero instead of the whole real line. However, the same solution method applies: using the additive property, one can show that there exists a real number $c_{ij}$ such that $f_{ij}(q) = c_{ij}q$ for every rational number $q$ inside the domain of $f_{ij}$. Then, using the continuity of $f_{ij}$ and the denseness of rational numbers in $\mathbb R$, we conclude that $f_{ij}(t)=c_{ij}t$.
Hence $f(t)=tC$ for some constant matrix $C$. That is, $U(t)=e^{tC}$ on some neighbourhood of zero. Thus $U$ is differentiable at zero.