Could two decidable languages ever not have a mapping reduction?
If you are talking about reduction in general (not polynomial reduction), then you basically can put all the logic in the reduction function. Suppose $L_1$ and $L_2$ are decidable languages. To reduce $L_1$ to $L_2$ we need a computable function $f$ such that $x\in L_1 \Leftrightarrow f(x)\in L_2$. The function $f$ just works as follows. Given a word $a\in L_2$ and a word $b \notin L_2$:


  $f(x) = \begin{cases} a &amp; \text{if } x \in L_1 \\ b &amp; \text{if } x \notin L_1 \end{cases}$


This function is computable because $L_1$ is decidable by assumption.

However, the above also points you to the exceptions. It assumes that there is a word $a\in L_2$ and a word $b\notin L_2$, and there exactly two languages for which this is not the case. Both of those languages are decidable.