One direction follows from the Cauchy Schwartz inequality:
$$|\langle Au,v\rangle| \leq \|Au\|\cdot\|v\| \\
\implies \sup\{|\langle Au,v\rangle| :\|u\|=\|v\|=1 \} \leq \sup \{\|Au\|: \|u\| = 1\} = \|A\|_{op}$$
The other direction is requires a little more work.
$$ \text{Let } S = \left\{\left|\left\langle Au,\frac{Au}{\|Au\|}\right\rangle\right| : \|u\|= 1\right\} \subset \{|\langle Au,v\rangle| :\|u\|=\|v\|=1\}$$
Then we note that the supremum of S must be less than the supremum of $\{|\langle Au,v\rangle| :\|u\|=\|v\|=1\}$. However we can note further that:
$$ \left|\left\langle Au,\frac{Au}{\|Au\|}\right\rangle\right| = \frac{1}{\|Au\|}
\langle Au,Au\rangle = \|Au\|\\
\implies \sup S = \sup \{\|Au\| : \|u\| = 1\} = \|A\|_{op}$$
And we get that
$$ \|A\|_{op} \leq \sup\{|\langle Au,v\rangle| :\|u\|=\|v\|=1\} $$