Could there exist a subfield $F$ of $\mathbb{R}$ such that $\pi$ is algebraic of, say degree 5 over $F$?
We know that $\pi$ is transcendental over $\mathbb{Q}$, hence $\mathbb{Q}(\pi)$ is not a field. right?
So, could there exist some other subfield of $\mathbb{R}$ such that $\pi$ is algebraic over that subfield?
Yes, consider the field $\mathbb{Q}[\pi^2]$, the subfield generated by $\pi^2$, it does not contain $\pi$ since $\pi$ is trancendental, $\pi$ is the solution of $X^2-\pi$.