Let it be that $\Omega$ is an uncountable set (e.g. $\Omega=\mathbb R)$.
I denote: $\mathcal A:=\{A\in\wp(\mathbb\Omega)\mid A\text{ is countable or is cocountable}\}$
Let it be that $E$ is not countable.
If $E\subseteq\bigcup_{n=1}^{\infty}A_n$ for $A_n\in\mathcal A$ then some integer $m$ must exist such that $A_m$ is not countable. Then $A_m$ must be cocountable so that $\sum_{n=1}^{\infty}\mu(A_n)\geq\mu(A_m)=1$. This observation justifies the conclusion that $\mu^*(E)\geq1$. We can take $A_1=\Omega$ and $A_n=\varnothing$ for $n\geq2$ and doing so we find that $\mu^*(E)\leq1+0+0+\cdots=1$. Proved is now that $\mu^*(E)=1$ whenever $E$ is not countable.
Let it be that $E$ is countable.
We have $E\subseteq\bigcup_{n=1}^{\infty}A_n$ for $A_1=E$ and $A_n=\varnothing$ for $n\geq2$, and if $E$ is countable then this is a union of sets in $\mathcal A$. This results in $\mu^*(E)\leq 0+0+\cdots=0$. From the definition of $E$ it follows that also $\mu^*(E)\geq0$ so we conclude that $\mu^*(E)=0$ whenever $E$ is countable.
If $E\notin\mathcal A$, i.e. $E$ is not countable and not cocountable then:$$\mu^*(\Omega)=1<1+1=\mu^*(E)+\mu^*(E^c)=\mu^*(\Omega\cap E)+\mu^*(\Omega\cap E^c)$$
This reveals that measurable sets are necessarily elements of $\mathcal A$, and - if I understand well - that $\mu^*$ is not a content on $\Omega$.
Let it be that $E$ is countable.
If $A$ is countable then:$$\mu^*(A)=0=0+0=\mu^*(A\cap E)+\mu^*(A\cap E^c)$$
If $A$ is not countable then:$$\mu^*(A)=1=0+1=\mu^*(A\cap E)+\mu^*(A\cap E^c)$$
Let it be that $E$ is cocountable.
If $A$ is countable then:$$\mu^*(A)=0=0+0=\mu^*(A\cap E)+\mu^*(A\cap E^c)$$
If $A$ is not countable then:$$\mu^*(A)=1=1+0=\mu^*(A\cap E)+\mu^*(A\cap E^c)$$
This because at least one of the sets $A\cap E$ and $A\cap E^c$ is not countable and $A\cap E^c$ is countable.
Proved is now that elements of $\mathcal A$ are measurable, and combined with the former conclusion that justifies the conclusion that $\mathcal A$ is exactly the collection of measurable sets.