First, make sure you work in the V-Ray Node Space. You can select it from the drop-down menu of the Node Space option.
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Then, go to the Create menu > Materials and select New Node Material option.
New Material node is created. When double-clicked on it, the Node Editor is opened. Now you can work within the Node Editor by creating and adjusting V-Ray nodes.
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For Cinema 4D version R25
Make sure V-Ray is your Renderer. This is done through Render Settings > Renderer.
Go to the Material Manager and from Create > Materials, select New Node Material.
The Node editor opens and you can now work with all available V-Ray nodes.
