If $V$ is a real Hilbert space, the bounded symmetric bilinear form $A$ does correspond to a bounded self-adjoint linear operator $T$ by $A(x,y) = <x, Ty>$, and your condition $A(v,v) \ne 0$ for $v \in V \backslash \{0\}$ says $T$ is injective. The range of $T$ is dense in $V$, but might not be closed, so it's not necessarily surjective. For example, the operator
on $L^2[0,1]$ given by $Tf(x) = x f(x)$ is self-adjoint and injective but not surjective, e.g. it doesn't contain the constant function $1$. In fact, a self-adjoint operator is
surjective if and only if its spectrum is bounded away from 0.
If $V$ is not a Hilbert space, all you get is a bounded operator from $V$ into its dual $V^*$.