$\newcommand{\li}{\operatorname{li}}$Yes, those values of $x$ are unbounded. As JoshuaZ indicates in a comment, the key here is Littlewood's result on sign changes, and because of the way $\pi(x)$ grows, it is easy to deal with jump discontinuities
without any difficult transcendence results. Here are the details.
Littlewood has proven that the difference $\pi(x)-\li(x)$ changes sign infinitely often, so there will be arbitrarily large $x_0$ such that $\pi(x_0)-\li(x_0)>0$. If we then consider the set of values on which this difference becomes nonpositive, this set will also be nonempty. Let $x_1$ be the infimum of this set. $\pi(x)-\li(x)$ is a right continuous function, so $\pi(x_1)-\li(x_1)\leq 0$. Moreover, if $x_1$ happened to be a jump discontinuity, then the left limit of $\pi(x)-\li(x)$ at $x_1$ would be $1$ smaller than its right limit, which would contradict $x_1$ being the infimum of the above set. So $x_1$ satisfies $\pi(x_1)=\li(x_1)$.