Right. With P8 anyway, the Library system still has certain limitations that appear to have lingered from older versions. You are also limited to saving poses only to the Pose library, materials to the Material library, etc. So if you have an outfit that's in the Characters library and you've placed all if its materials in a subdirectory under the outfit called Mats for example, you can't save a material in the Mats subdirectory; you have to save it somewhere in the Materials library. After that you can move it anywhere you want with Explorer, but you have to save it to wherever Poser expects it to be saved.

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OS: Windows 10 64-bit, Poser: 10