First, realize that the word 'natural' carries about as much meaning as the word 'obvious'. Don't let the word intimidate you.
Remember that $\psi^*:W^* \to V^*$, so if $w^* \in W^*$, then $\psi^*(w^*) \in V^*$.
Now select $v \in V$, and apply $\psi^*(w^*) $, ie, make sense of $(\psi^*(w^*))(v)$, remembering that $\psi(v) \in W$.
The only way it 'fits' together is $w^*(\psi(v))$.
Rudin uses the suggestive notation $\langle v, \psi^*(w^*) \rangle$ for $(\psi^*(w^*))(v)$.
The above then reads $\langle v, \psi^*(w^*) \rangle = \langle \psi(v), w^* \rangle $, which fits well with the Hilbert space notation.