The answer to the question is: not really.
Consider $G=\mathbb{R}^n\,.$ This has nontrivial group cohomology in all degrees $\le n$ (by the van Est isomorphism theorem, for example), while the classifying space is the point $*\,,$ which has vanishing de Rham cohomology in positive degrees. Therefore, there is certainly no surjection from the de Rham cohomology to the group cohomology.
On the other extreme, consider $G=T^n\,.$ This has vanishing group cohomology in positive degrees (since it's compact), while it has nontrivial de Rham cohomology in all degrees $\le n\,,$ therefore there is no such injection either.
The only relation I know of is that if your group $G$ is compact and has vanishing homotopy groups up to and including degree $n\,,$ then both cohomologies vanish up to degree $n$ (again, by the van Est isomorphism theorem). However, if $n\ge 3$ then this implies that $G$ is a point, by the result in this question: https://math.stackexchange.com/questions/960372/a-question-about-contractibility-of-a-lie-group
There isn't even a strong relationship between group cohomology of $G$ and the cohomology of $BG\,.$ There is one, in a sense, but it's more complicated. If $G$ is discrete however, the group cohomology of $G$ is isomorphic to the cohomology of $BG$ with coefficients in the discrete group $\mathbb{R}\,.$ For nondiscrete Lie groups $G$, there is an analogue to this isomorphism, but it's more complex and involves $EG\,.$
Note: when I say group cohomology I am strictly speaking of the cohomology of group cocycles valued in the Lie group $\mathbb{R}\,,$ however you can consider group cohomology valued in any abelian group.