V is sometimes the symbol for electric potential, which is just electric potential energy per unit charge:
[tex][\textrm{potential}] = \frac{[\textrm{energy}]}{[\textrm{charge}]}[/tex]
The unit for potential, is of, course, the joule per coulomb, also known as a volt (whose symbol is also V).
[tex]1 \ \textrm{V} = 1 \ \frac{\textrm{J}}{\textrm{C}}[/tex]
So, the symbol V is being used both for the physical quantity known as potential, AND for the units in which it is measured. Note, however, that symbols for physical quantities and mathematical variables are typically italicized when typeset properly, whereas unit symbols are not, so that we might have something like:
[tex]V = 5 \ \textrm{V}[/tex]
It's obvious why the UNIT symbol is a V (the unit is volt, after all, named after Volta). It's less obvious why the symbol for potential is a V. It could be because a difference in electric potential (or potential difference for short) is often referred to as a voltage. Calling voltage V is intuitive. Then again, the symbol for a physical quantity doesn't have to make intuitive sense. Why is p momentum?. Heck, sometimes we use greek letters.