Suppose I have an open subset $\Omega\subseteq {\mathbb R}^n$ and a smooth (i.e. in $C^\infty$) injective mapping $i: \Omega\to {\mathbb R}^N$ where $N\geq n$. Does this mean that there is a smooth mapping $f: A\to \Omega$ such that $A\supseteq i(\Omega)$, $A$ is open in ${\mathbb R}^N$ and $f|_{i(\Omega)} = i^{-1}$.
It can be shown that $\Omega$ and $i(\Omega)$ are are diffeomorphic as smooth manifolds. Argument: there is a single chart on $\Omega$, $(\Omega, {\rm id})$ and a single chart on $i(\Omega)$, i.e. $(i(\Omega), i^{-1})$. It is easy to see that $i: \Omega\to i(\Omega)$ is a $C^\infty$ mapping between smooth manifolds $\Omega$ and $i(\Omega)$, and its inverse $i^{-1}: i(\Omega)\to \Omega$ is also $C^\infty$ mapping.
Thus, $\Omega$ and $i(\Omega)$ are diffeomorphic. Does this mean that there is a smooth mapping $f: A\to \Omega$ such that $A\supseteq i(\Omega)$, $A$ is open in ${\mathbb R}^N$ and $f|_{i(\Omega)} = i^{-1}$.

You need some additional assumptions on the set $\Omega$ at least. Consider the case when $\Omega$ is not connected, then if $A$ is connected, $i^{-1}$ can't be extended even to the continuous mapping of $A$.