Put simply: YES!
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We have made sure it is easy-peasy to access your library of content.

When you're scheduling posts for Facebook, we’ve made sure your full media collections are available so you’re not having to upload your work twice, yuck!

All you have to do is make sure you have both your Instagram Business/Creator account and the connected Facebook Business Page set up inside your Plann workspace.
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Then, when you want to grab assets to use in Facebook or Instagram you can simply go to Media Collections and boom you're ready to go!