Suppose $X$ is a complex manifold, we have the map $H^0(X,K_X^*/O_X^*)\to H^1(X,O_X^*)$, is the canonical line bundle $\wedge^n{\Omega}$ always in the image of the map?

The answer is no. The group $H^0(X, \mathcal{K}_X^*/\mathcal{O}_X^*)$ is isomorphic to the divisor group $\mathrm{Div}(X)$ (see e.g. Huybrechts' Complex Geometry, Prop. 2.3.9), so its image in $\mathrm{Pic}(X)$ is the group of line bundles associated to some divisor. Now there are complex compact surfaces which do not contain any curve but with a nontrivial canonical bundle, for instance the Inoue surfaces (see Barth et al., ch. V, §19). 


Perhaps I did not get you question. Anyway, $H^{1}(X,\mathcal{O}_X^{*})\cong Pic(X)$. If $X$ is an integral schemes the Picard group is isomorphic to the class group of Cartier divisors. Therefore one can interpret $\bigwedge^n\Omega_X$ both as a line bunlde on $X$ and as a Cartier divisor $K_X$ in $X$. Does this answer to your question? 

