The following is a fact in Murphy's C*-algebras and operator theory page 49:
Suppose $u,v \in B(H)$, where $H$ is a Hilbert space, then $u=v$ if and only if $\langle u\xi,\xi\rangle = \langle v\xi,\xi\rangle$ for all $\xi \in H$.
Clearly if $u=v$ then $\langle u\xi,\xi\rangle = \langle v\xi,\xi\rangle$ for all $\xi\in H$. For converse, I should show $\langle u\xi,\eta\rangle=\langle v\xi,\eta\rangle$ for all $\xi,\eta\in H$, while I can not show it. I think about Polarisation identity but I can not use it. Please help me. Thanks in advance.
This is a corollary of the previous statement in the book: the polarization identity says that for a sesquilinear form $\sigma$, you can write $$4\sigma(x,y) = \sigma(x+y,x+y)+i\sigma(x+iy,x+iy) - \sigma(x-y,x-y) -i\sigma(x-iy,x-iy).$$ In particular, this shows that given two sesquilinear forms $\sigma, \sigma'$, if $\sigma(v,v) = \sigma'(v,v)$ for all $v$, the RHS is the same if you replace $\sigma$ and $\sigma'$; so $\sigma'(x,y) = \sigma(x,y)$. Thus it suffices to check if $\sigma = \sigma'$ on pairs $(v,v)$.
It's easy to check that the maps $\sigma(x,y) = \langle ux, y\rangle$ and $\sigma'(x,y) = \langle vx, y\rangle$ are sesquilinear forms. By hypothesis, you know that $\sigma(x,x) = \sigma'(x,x)$ for all $x$; so by the above discussion, $\sigma(x,y) = \sigma'(x,y)$ for all $x,y$. Rewriting this, we have $\langle (u-v)x, y \rangle = 0$ for all $x,y$; so picking $y = (u-v)x$, we see that $\|(u-v)x\|^2 = 0$, and thus that $(u-v)x = 0$. So $u=v$ as desired.
(This is really just a rephrasing of what Murphy wrote.)