Can I book a sunset wine tasting for the middle of October?
October is last month of the season. Call and ask.
Yes book a few days ahead
When we arrived, an employee greeted us and asked if we had booked a tour and we had not. So I am guessing that you could book a wine tasting at sunset. They seemed very accommodating.
Probably but the only people that can answer that would be the winery. As an alternative try to Google it.
Get quick answers from Venetsanos Winery staff and past visitors.