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The Material Override section in V-Ray Settings is where you can specify a color or

material to be used to override all other materials in the scene.

Starting with V-Ray 7, you can preserve specific material properties and use predefined presets for overriding.

Material Override – When enabled, this option allows the user to you can override the scene materials when rendering. All objects are rendered with the override material selected, or with a default material using the Override Color for diffuse shading.

Override Mode – Determines the override material mode. 

Color – A diffuse material with the specified color is used. 
Material – The selected scene material is used.
Preset – A predefined material is used. The available presets are: White, Arctic, Clay, Dark Clay, Plastic, and Wood. See the example for a preview.

Split Refractive – Enables a custom override option for all refractive materials.

Color – (Available when Override Mode is Color) Specifies the color of the default override material. If a material is selected from the drop down menu below, this color is ignored. See the example for a preview.

Material – (Available when Override Mode is Material) Specfies the material to override the original project Override Material – Overrides the scene materials when rendering. All objects are rendered with the selected material selected material applied. Materials with the option "Can be Overridden" disabled are not affected. See the example for a preview.

Refractive Color – Specifies the color of the material to override the refractive project materials when rendering.

Round Edges – (Available when Override Mode is Preset) When enabled, edge rounding is applied to the override material.

Effects Scale – (Available when Override Mode is Preset) Scales the dirt and edge rounding radiuses as well as the size of the texture/s of the override material. Can be used when the default effects size doesn't work well in the current project.