A skunk will almost always spray when it is killed and your best bet for not getting sprayed is of course, for you to be a good distance away.

Will a skunk spray when shot in the head?

If you head shoot them, they short circut and spray, they can't help it. Most times if I shot a skunk behind the shoulder through the lungs they did not spray, sometimes a little leaked out when they died but most times they didn't spray.

Can skunks spray when picked up?

The muscles involved rely on raising the tail. So, if you catch a skunk under a heavy blanket, or in a trap or a low box they can't lift their tail and they can't spray. ... A grizzled old trapper had told him that if you pick up a skunk by the tail, they can't spray you.