The claim is false. $\emptyset$ cannot be reduced to its complement $\Sigma^*$ (and vice-versa).
However, if you restrict yourself to languages $L$ such that $L \not\in \{ \emptyset, \Sigma^*\}$ then it is true that $L \le \overline{L}$. To see this let $n$ be any fixed element of $L$ and let $y$ be any fixed element of $\overline{L}$. Such elements exist by our choice of $L$.
The reduction is given by:
$$
f(x) = \begin{cases}
y & \mbox{if } x \in L \\
n & \mbox{if } x \not\in L
\end{cases}.
$$
Notice that $f$ can be computed in polynomial time since $L \in \mathsf{P}$, which means that we can decide in polynomial time whether $x \in L$.