Yes, but only if you’re creative. Pure vinegar won’t make spiders pack their bags and leave your house forever. Spiders aren’t reading your cleaning schedule.
If you spray a spider directly with a 50/50 mix of water and white vinegar, it will freak out. It may freeze, curl up, or scram. It’s basically a chemical panic button.
But here’s the hilarious part: the smell fades fast. Within an hour or two, the vinegar evaporates. The spider comes back. It has a terrible memory for vinegar.
So no, a quick spritz on your windowsill won’t build a force field. You’d have to reapply every single day. Are you that dedicated to spider warfare? Probably not.