To create a material, simply open the open the Materials tab in Rhino, or type 'Materials' into the Rhino command line. Click on the large + symbol and then choose 'Enscape' as the material Type.
I think Toscano is referring to a faster method to open the right material by just clicking on it with an eyedropper in the enscape render window.
That would save a TON of time in my opinion. You can vote for the suggestion on the voting portal here: https://portal.productboard.co…ge-materials-from-enscape