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The Material Override section in V-Ray render settings is where you can specify a color or a material to be used to override all other materials in the scene. 



UI Path: ||V-Ray Asset Editor|| > Render Settings > Material Override rollout




Material Override – Enable Material Override. 

Override Color – Specifies the color of the default override material. If a material is selected from the drop down menu below, this color is ignored. 

Override Material – Overrides the scene materials when rendering. All objects are rendered with the selected material applied. Materials with the option "Can be Overridden" disabled will not be affected.