First of all, the isomorphisms $V\cong V^*$ and $V\cong V^{**}$ only hold (in general) for finite dimensional $K$-vector spaces. If $V$ does not admit a finite basis, the isomorphisms may fail.
For an isomorphism $V\to V^*$ you have to specify how a vector $v\in V$ should act as a linear form $V\to K$. It turns out that this amounts to specifying a non-degenerate bilinear form $\langle-,-\rangle\colon V\times V\to K$ and send $v\in V$ to $\langle v,-\rangle\in V^*$, i.e., the linear form sending $w$ to $\langle v,w\rangle$. Another way to achieve the same thing is by picking a basis $e_1,\dots,e_n$ and declaring it to be orthonormal, hence defining a bilinear form with $\langle e_i, e_j\rangle = \delta_{ij}$. In this case you get a dual basis $e_i^* = \langle e_i, -\rangle$.
To summarize, in order to construct an isomorphism $V\to V^*$, you have to either choose a basis of $V$ or a non-degenerate bilinear form.
Now for an isomorphism $V\to V^{**}$, you have to specify how a vector $v\in V$ acts as a linear form $V^*\to K$. So given a linear form $\omega\in V^*$, how does $v\in V$ act on $\omega$ to produce an element of $K$? In this situation it is just natural to just apply the linear form $\omega$ to the vector $v$. Hence, the isomorphism $V\to V^{**}$ sends $v\in V$ to the linear form $V^*\to K$ with $\omega\mapsto \omega(v)$.
We see that we did not need to make any choices in writing down this isomorphism $V\to V^{**}$.
To answer your question, if you use "$V=V^{**}$" to denote the identification of $V$ and $V^{**}$ under the above natural isomorphism, you can not write "$V=V^*$" in the same spirit, since any isomorphism $V\to V^*$ requires you to make some (arbitrary) choices.