The question is ``isomorphic as what?''. It is obvious that $\mathcal{O}_G \cong \mathbb{Z}[G]$ as $\mathbb{Z}$-modules because they are $\mathbb{Z}$-modules of the same rank.
However, we want to compare these objects with their multiplication and comultiplication structures. You should be able to convince yourself that $\mathcal{O}_G$ and $\mathbb{Z}[G]$ cannot be isomorphic as rings.
For example let $G =\{ e, \sigma \}$ with $\sigma^2 = e$. Then both $\mathbb{Z}$-modules have a basis $e,\sigma$.
In $\mathcal{O}_G$ we have $(a e + b \sigma)^2 =a^2 e + b^2 \sigma$ so $e$ and $\sigma$ are idempotents.
In $\mathbb{Z}[G]$ we have $(a e + b \sigma)^2 = (a^2 + b^2) e + 2 ab \sigma$
so if $(a e + b \sigma)$ is idempotent then $a = a^2 + b^2$ and $b = 2 ab$ so either $b = 0$ and $a = 1$ or $a = 0$ and $b = 0$. Therefore there are only trvial idempotents in this ring.
However, these objects have more structure, they are Hopf algebras meaning they also carry a compatible comultiplication structure (you wrote down the comultiplication $m$ for $\mathcal{O}_G$ and for $\mathbb{Z}[G]$ this is given by $u_g \mapsto u_g \otimes u_g$). Then it turns out that $\mathbb{Z}[G]$ and $\mathcal{O}_G$ are dual Hopf algebras, $\mathbb{Z}[G] = (\mathcal{O}_G)^*$. You can think of this operation as ``swapping multiplication and comultiplication'' if that makes it easier to visualize what is going on. The isomorphism takes $u_g \mapsto (e_g \mapsto 1)$ which makes sense thinking of $\mathbb{Z}[G]$ as functions on G
We can promote this to a duality of finite locally free group schemes. Saying that on the functor of points,
$$ G^\vee(T) = \mathrm{Hom}_{\text{Grp}_T}(G_T, \mathbb{G}_m) $$
Then we see that $\mathrm{Spec}(\mathbb{Z}[G])$ is the dual group to $G_{\mathrm{Spec}(\mathbb{Z})}$
For example, if $G = \mathbb{Z}/n \mathbb{Z}$ then $\mathbb{Z}[G] = \mathbb{Z}[x]/(x^n - 1)$ so,
$$ G_{\mathrm{Spec}(\mathbb{Z})}^\vee = \mathrm{Spec}(\mathbb{Z}[G]) = \mathrm{Spec}(\mathbb{Z}[x]/(x^n - 1)) = \mu_n $$
is the group of $n^{\text{th}}$-roots of unity.