There is no equivalence (or 'bi-implication'), only the following implication:
> **If** $G$ is a group acting on a non-empty set $A$, **then** the relation $\sim$ on $A$ defined by $$a\sim b\qquad\Leftrightarrow\qquad (\exists g\in G)(a=gb),$$ is an equivalence relation.
The ' **iff** ' in your question only serves to define the relation on $A$.