Since V-Ray works best with *.vismat files, use a free script:
You will see ads for a 100GB "Ultimate V-Ray Library" for free. Don't do it. These are either: Sketchup Vray Material Library Free Download
Searching Google for "V-Ray Material Library free download full version" often leads to: Since V-Ray works best with *
The bottom line: It is 100% possible to render photorealistic images with V-Ray using free textures and manual setup. However, for the official drag-and-drop library of 500+ assets, you must purchase a license or start a free trial. The bottom line: It is 100% possible to
Go to these websites (all legal & free for commercial use):
Here are the best, safest places to get high-quality V-Ray materials for $0.