One of the chaps I work with made some barley risotto last night, and said it was great. I've been meaning to try it out myself for a while and finally did so tonight.
Started off by sauteing some onions, added and sauteed brown mushrooms and a dash of minced garlic, then added the barley and cooked it all for another couple minutes before pouring in the first round of stock. I just used 1 "vegetable" stock cube in about 1.5 litres of water and found that to be a good amount of seasoning (didn't add salt at the end). Proceeded with the regular risotto technique until it was sufficiently creamy. Then I added chunks of half a roasted butternut squash, and some steamed snow peas.
The result was quite nice. I'm amazed that barley is such a perfect substitute for arborio...