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On your vray toolbar, click on vray material browser (see image below)
The above browser will bring you to Chaos Cosmos Browser, press the sign-in button located on the upper right side. Create an account with them for you to fully use those assets
If by any chance, you did not fully install the material library during the installation (because it's optional), go to C:\Program Files\Chaos Group\V-Ray\3ds Max NNNN\bin
or in C:\ProgramData\Autodesk\ApplicationPlugins\VRay3dsMax2022\bin.
and look for mtllib.exe Double-click it to install your offline material library. After installation, click once again the vray material button as shown on the previous comments.
This is the preview of the vray material browser in an Online mode, to use, just right click on the choosen material, and select your preference (1) if you select an object first, then you can use to selected objects (2) if no selected object, then you can use add to material editor
Sorry for my multiple responses, I just made it sure that I presented my answers to your query.
More info here: V-Ray Material Library Browser
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