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Sorry for the late reply, we just came by this post.
By unfollowing the podcast it should disappear from Your Library. You can unfollow it by going to Your Library > Podcasts and pressing and holding on the podcast (right-clicking if you're on desktop) > Unfollow.
If the issue persists, feel free to send over a screenshot / screen recording which shows how things look on your end.
Hey there @ninthwitch,
Thanks for the reply and the video recording.
This is most likely an issue with the cache on the phone. First of all, try opening the podcast page and unfollowing the podcast. If that doesn't work and the podcast page doesn't exist, run a clean reinstall of the app. You can follow this Guide, where you'll find instructions on how to remove all app data and cache, before reinstalling. This usually takes care of similar issues. Since the podcast was removed, it should disappear from your library eventually, unfortunately we can't say exactly when.
Note: clearing the app data and cache will remove your content downloaded for offline listening, so you'll need to re-download once you reinstall the app.
Let us know how it goes.