The key is to see how $T$ acts on an arbitrary basis. Suppose $\langle Tx,x \rangle = 0$ for all $x \in V$, where $V$ is a (real or complex) vector space.
If $T$ acts on a real space with (Hamel) basis $\{e_j\}_{j \in \alpha}$, then we have
- $\langle e_j, Te_j \rangle = 0$
- $
\langle e_j + e_k, T(e_j + e_k) \rangle = 0 \implies
\langle e_j, T e_k \rangle = -\langle Te_k, e_j \rangle
$
This is enough to deduce that $T = -T^*$. If $T$ acts on a complex space, we have the additional constraint
- $
\langle e_j + ie_k, T(e_j + ie_k) \rangle = 0 \implies
\langle e_j, T e_k \rangle = \langle Te_k, e_j \rangle
$
This, together with the other two properties, allows us to deduce that $T = 0$.
We deduce that on a real space, $\langle Tx,x \rangle = 0$ for all $x \in V$ $\iff T^* = -T$, and on a complex space, $\langle Tx,x \rangle = 0$ for all $x \in V$ $\iff T = 0$.
Note: I haven't explicitly proved the converse in either case. I think that you'll find that, in each case, the proof is straightforward.
While I can't say whether the result is deep, I can say that this shows that the inner product becomes much more powerful over complex spaces.
A consequence of this quirk is that when one defines positive definite operators over a real inner product space, it is significant whether one specifies that the operator must also be self-adjoint. As real bilinear forms, matrices act the same up to their self-adjoint part. That is, we have $A + A^*= B + B^* \iff \langle x,Ax \rangle = \langle x,Bx \rangle$ for all $x$.
For complex inner-product spaces, the additional specification of self-adjointness is redundant, and we have $A = B \iff \langle x,Ax \rangle = \langle x,Bx \rangle$ for all $x$.
Another interesting quirk: the statement
$$
\|x+y\|^2 = \|x\|^2 + \|y\|^2 \iff \langle x,y \rangle = 0
$$
is only true for real inner-product spaces.