I am fairly certain there are some inaccuracies on this page, and since an answer has already been accepted and upvoted I would like to try to address them. This post only addresses the infinite dimensional case, since everything is fine over finite dimensional spaces.
$V^*\otimes W^* \cong (V\otimes W)^*$
OK this is true, they have the same dimension, but I want to point out that the natural map $V^*\otimes W^* \hookrightarrow (V\otimes W)^*$ is never an isomorphism. Neil Strickland has written an extremely pleasant proof over on mathoverflow.
Especially in the case we care about, $A^*\otimes A^*$ vs $(A\otimes A)^*$ one can check that $\dim(A^*\otimes A^*) = \dim (A\otimes A)^* = \dim A^*$, but this doesn't give us any meaningful way identifying the two spaces.
the multiplication $m: A\otimes A \to A$ and unit $k\to A$ maps on an algebra A give rise to comuliplication $A^*\to A^*\otimes A^*$.
This is false. The multiplication dualizes to a map $A^* \to (A\otimes A)^*$ which in general does not factor through $A^*\otimes A^* \subseteq (A\otimes A)^*$. Sometimes it does, such as if $m$ is the zero map (allowable in a non-unital algebra). For $A = k[x]$ it does not. In general, for any $A$ there is a coalgebra structure on an appropriate subspace $A^\circ \leq A^*$, which for finite dimensional $A$ is just $A^\circ = A^*$. A good reference for this is Section 2.5 of Radford's Hopf Algebras - the definition is actually just $A^\circ = (m^*)^{-1}(A^*\otimes A^*)$. In the case of $k[x]$ see for example Exercise 2.5.17 of Radford.
$k[[x_1]]\otimes\cdots\otimes k[[x_n]] \cong k[[x_1,\cdots,x_n]]$ just as for polynomial algebras.
For polynomials, the isomorphism $k[x]\otimes k[y] \to k[x,y]$ is multiplication. For power series, the map of multiplication is not an isomorphism. In other words, completion does not commute with tensor products (see e.g. this mse question).
Upon identifying $A^* = k[[x]]$, The injection $A^*\otimes A^* \to (A\otimes A)^*$ is identified with the map of multiplication $k[[x_1]]\otimes k[[x_2]] \to k[[x_1,x_2]].$ As an example of something not in the image of this map we borrow from Strickland's overflow post the power series $$1 + x_1x_2 + x_1^2x_2^2 + x_1^3x_2^3 + \cdots = \sum_{i=0}^\infty (x_1x_2)^i.$$ Strickland has already provided a beautiful proof, but perhaps I can offer an explanation (not a proof!) why this is not in the image. It is easier to see this is not in the image of the map $A^*\times A^* \to (A\otimes A)^*$, namely to have $$(a_0 + a_1x_1 + a_2x_1^2 + \cdots )(b_0 + b_1x_2 + b_2x_2^2 + \cdots ) = \sum_{i=0}^\infty (x_1x_2)^i$$ we must solve equations $a_ib_j = \delta_{ij}$ for all $i,j\geq 0$. But $a_1b_1 = 1, a_2b_2 = 1$ and $a_1b_2 = 0$ are already contradictory, and in fact no matter what you do infinitely many pairs $(i,j)$ will have $a_ib_j \neq \delta_{ij}$. Now, in $A^*\otimes A^*$ you actually get to have finite sums of elements from $A^*\times A^*$, which allows you to try a little harder to solve more of the equations $a_ib_j = \delta_{ij}$. But the moral is that just having finite sums won't let you fix the infinitely many problems you have.
However, $k[[x_1,x_2]]$ is a completed tensor product, i.e. $k[[x_1,x_2]] = k[[x_1]]\hat\otimes k[[x_2]]$. The meaning of this is that $k[[x_1]]\otimes k[[x_2]]$ is a local ring (mathoverflow) with maximal ideal $\mathfrak m = (x_1\otimes 1, 1\otimes x_2)$; and the $\mathfrak m$-adic completion is isomorphic to $k[[x_1,x_2]]$.