The skip is \bigskipamount; \bigskip is a \vskip of \bigskipamount, so you could use
\setlength{\itemsep}{\bigskipamount}
Of course, you can say
\setlength{\itemsep}{12pt plus4pt minus4pt}
For the record, the definitions in Plain:
\newskip\smallskipamount % the amount of a \smallskip
\smallskipamount=3pt plus1pt minus1pt
\newskip\medskipamount % the amount of a \medskip
\medskipamount=6pt plus2pt minus2pt
\newskip\bigskipamount % the amount of a \bigskip
\bigskipamount=12pt plus4pt minus4pt
\def\smallskip{\vskip\smallskipamount}
\def\medskip{\vskip\medskipamount}
\def\bigskip{\vskip\bigskipamount}
and in the LaTeX kernel:
\def\smallskip{\vspace\smallskipamount}
\def\medskip{\vspace\medskipamount}
\def\bigskip{\vspace\bigskipamount}
\newskip\smallskipamount
\smallskipamount=3pt plus 1pt minus 1pt
\newskip\medskipamount
\medskipamount =6pt plus 2pt minus 2pt
\newskip\bigskipamount
\bigskipamount =12pt plus 4pt minus 4pt