Yes, use the small cleat alongside the windlass. Tie your rolling hitch on the chain, letting it go out through the bow roller and tie the bitter end off (counterclockwise) around the cleat with a cleat hitch, making sure the tension is off the windlass. Of course if you are into your rope rode, just tie that off. Alternatively, you can use a bridle with a chain hook and bring it through the chocks to the large cleat.
Edit: I see that there was a recent thread/controversy on this about a month ago, at least regarding other models. I have always used the small cleat alongside the windlass when at anchor to tie off the rode. I see no other purpose for it. The bow roller has a bale to keep the anchor from being prematurely released and, at least on the R-31, the cleat does not seem in a good position for simply tying a safety hook. I have assumed that the whole small platform which carries the windlass and both the large and small cleats is reinforced and capable of carrying the loads. However some people, at least on other models, are tying off the rode to the large cleat aft of the windlass, even though it seems awkward.
So maybe someone from the factory can comment on recommended procedure for tying off the anchor rode...?
John