Following the \index quoting rules (prepend a reserved character with a double-quote), I do
\index{"|"| operator}
but the entry never shows up in the index. Doing these (similar) things does work as expected:
\index{"!"! operator}
\index{"| operator}
So what is special about ||? Needless to say, it also doesn't work without double-quotes.
It seems that this only happens when the hyperref package is used.