The correct version of your statement is the following. Let $K$ be a commutative ring and suppose that $V,W$ are (left) $KG$-modules with $V$ finitely generated projective over $K$. Then $$\mathrm{Ext}_{KG}^n(V,W)\cong H^n(G,\hom(V,K)\otimes_K W).$$
The proof is like this. If $A,B$ are $KG$-modules, then $\hom_K(A,B)$ is a $KG$-module with $G$ acting by conjugation. Moreover, $$\hom_{KG}(K,\hom_K(A,B))\cong \hom_K(A,B)^G\cong \hom_{KG}(A,B).$$ Take an injective resolution $W\to I_\bullet$ over $KG$. Then $\hom_{KG}(V,I_\bullet)\cong \hom_K(K,\hom_K(V, I_\bullet))$. Notice that since $\hom_K(V,-)$ is exact because $V$ is $K$-projective, we have that $\hom_K(V,W)\to \hom_K(V,I_\bullet)$ is a resolution. It is straightforward to check that if $I$ is an injective $KG$-module, then there is a natural isomorphism $\hom_{KG}(-,\hom_K(V,I))\cong \hom_{KG}(-\otimes_K V,I)$, and hence this functor is exact, as $V$ is $K$-projective and $I$ is injective. Thus $\hom_K(V,I)$ is injective. It follows that $\hom_K(V,W)\to \hom_K(V,I_\bullet)$ is an injective resolution. Taking cohomology we see that $$\mathrm{Ext}^n_{KG}(V,W)\cong \mathrm{Ext}^n_{KG}(K,\hom_K(V,W))\cong \mathrm{Ext}^n_{KG}(K,\hom(V,K)\otimes_K W)$$ since $V$ is a finitely generated projective $KG$-module.
It remains to observe that if $M$ is a $KG$-module, then $\mathrm{Ext}^n_{KG}(K,M)\cong H^n(G,M)$. For this, take a free resolution $F_\bullet\to \mathbb Z$ over $\mathbb ZG$. Notice that $H_n(K\otimes_{\mathbb Z} F_\bullet)\cong \mathrm{Tor}^{\mathbb Z}_n(K,\mathbb Z)$ since each free $\mathbb ZG$-module is a free $\mathbb Z$-module. We conclude that $H_n(K\otimes_{\mathbb Z}F_\bullet)=0$ for $n\geq 1$ and is $K$ when $n=0$. Thus $K\otimes_{\mathbb Z}F_\bullet$ is a free resolution of $K$ over $KG$. Therefore, $$H^n(G,M)\cong H^n(\hom_{\mathbb ZG}(F_\bullet,M))\cong H^n(\hom_{KG}(K\otimes_{\mathbb Z}F_\bullet,M))\cong \mathrm{Ext}^n_{KG}(K,M).$$
One can generalize this argument to show that if $V$ is a finitely generated projective $K$-module and $U,W$ are $KG$-modules, then $\mathrm{Ext}^n_{KG}(U\otimes V,W)\cong \mathrm{Ext}^n(U,\hom_K(V,K)\otimes W)$, where $U=K$ in the previous case.
Of course, if $K$ is a field then any finite dimensional $KG$-module is $K$-projective.