Any and all calls that connect will show up in your usage details. VZW-VZW calls, Night & Weekend calls and Friends & Family calls all will show up. You need to pay attention to the "usage type" column, if it says M2M, Off-Peak or N&W then those calls are not deducting from your airtime. Only calls that show up as "Plan Allow" will deduct from your minutes.
If you're looking at your usage under the MyServices tab under MyUsage then no, you won't see that. For your unbilled usage there's no way to see what type of call it is or if it's using your minutes.
You will be able to see the usage type on your bill to confirm your Friends & Family numbers aren't using minutes, they will show up on the bill as M2M.