The answer is $1/4$. For any probability distribution on $[0,1]$ the point $p=(EX,EX^2)$ will be a point in the convex hull of the set $S = \{(x,x^2):x\in[0,1]\}$. (This is a segment of a parabola.) The variance is the height of $p$ above the set $S$. This is clearly maximized when $p$ lies on the straight line connecting $(0,0)$ to $(1,1)$. By calculus, this is attained at $p=(1/2,1/2)$, which is $1/4$ above the point $(1/2,1/4)\in S$.
That $p$ is in the convex hull of $S$ is a consequence of Caratheodory's theorem: each element $p$ of the convex hull of $S$ is a weighted combination of at most 3 elements of $S$: Let that combination be $p=\sum_{i=1}^3 w_i\cdot(x_i,x_i^2)$, where the $w_i\ge0$ add up to $1$. Now look at the prob distribution for which $PX=x_i)=w_i$.
Its first 2 moments are the components of $p$.
In the special case at hand Caratheodory's theorem is trivial.
Every point in the convex hull of $S$ is on a chord of $S$.
If $p$ is already in $S$, it is of the form $p=(x,x^2)$, and the prob law $P(X=x)=1$ does the trick. Otherwise, the line passing through $(0,0)$
and $p$ cuts $S$ at $q$; the chord in question can be between $(0,0)$ and $q$, and $a$ can be chosen so $P(X=(0,0))=a, P(X=q)=1-a$ does the trick.
More generally, as a comment suggests, this is a fundamental property of a expectation operator. An expectation $ET(X)$ of a vector valued function is a particular weighted average of the possible values of the function $T(x)$. A probability law, one can think, amounts to a choice of weights. In problems like this one, the set of possible values of $ET(X)$ you get as you vary the probability law of $X$ is the convex hull of the set of values of the function $T(x)$.