Let M be a smooth manifold. I was wondering if every finite or infinite CW complex has the homotopy type of a smooth manifold because it seems way easier to compute De Rham cohomology groups than homology groups.
If the answer to the questions are yes, is it hard to find a smooth approximation of a CW complex?
This is a partial answer.
If $X$ is a finite CW-complex, then in general there does not exist a compact manifold which is homotopy equivalent to $X$.
It clearly suffices to consider connected CW-complexes because we can argue componentwise.
So let $X$ be a finite connected CW-complex of dimension $n$ such that its $n$-th homology group with coefficients in $\mathbb Z_2$ has the property $H_n(X;\mathbb Z_2) \ne \mathbb Z_2$. An example is $S^n \vee S^n$. Assume that $X$ is homotopy equivalent to a compact manifold $M$ of dimension $m$. It must clearly be connected. A well-known fact (see e.g. Hatcher Theorem 3.26) is that $H_k(M;\mathbb Z_2) = 0$ for $k > m$ and $H_m(M;\mathbb Z_2) = \mathbb Z_2$. Hence $n \ge m$ is impossible. But also $n < m$ is impossible because in that case $H_m(X) = 0$.
This leaves open whether there always exists a non-compact manifold $M$ which is homotopy equivalent to $X$. In the example $X = S^1 \vee S^1$ this is the case.
Update:
In Moishe Kohan's answer you see that the answer is "yes" for finite (connected) CW-complexes and non-compact (connected) manifolds. Note that if $X$ is homotopy equivalent to such $M$, then necessarily $\text{dim} M > \text{dim} X$ provided $H_{\text{dim} X}(X) \ne 0$. See Hatcher Proposition 3.29.