The Borel sigma algebra on $\mathbb{R}^n$ is obtained by starting with open sets and repeatedly applying the operations of complement, countable union, countable intersection. Now Henri Lebesgue famously made the mistake of thinking that the projection of a Borel set is always a Borel set. In reality, the projection of a Borel set need not be a Borel set, although it is still Lebesgue measurable. So that is a way of constructing a Lebesgue measurable set that is not a Borel set.
But my question is, what is an example of a Lebesgue measurable set that cannot be constructed in this way? That is, what is a Lebesgue measurable set that cannot be constructed by starting with open sets in $\mathbb{R}^n$ and repeatedly applying the operations of complement, countable union, countable intersection, and projection?
Start with a set $A$ of measure zero. Choose some insane subset $B\subseteq A$ (e.g. a Bernstein set if $A$ is closed, or a Vitali set if it makes sense). Then $B$ is Lebesgue measurable, but not analytic.
Also, somewhat trivially (relative to the fact that analytic sets are measurable), every coanalytic set is Lebesgue measurable (in particular, a coanalytic, non-Borel set is not analytic, but measurable). Similarly, every countable Boolean combination of analytic sets is measurable.
More generally, every Lebesgue measurable (or, indeed, measurable with respect to any given regular measure) is of the form $G\mathbin\triangle N$, where $G$ is a $G_\delta$ set and $N$ is of measure $0$. It will be as well behaved as $N$ is (more or less).
Note that you cannot give an "explicit" example, as without axiom of choice, it is consistent that every set of reals is Borel (or even a countable union of countable sets).