Yes, I have baked with barley flour.
It was delicious, both mixed with other flours and on its own.
The loaves were nicely textured, pleasantly flavoured, and no one knew that it was barley unless I told them. They just thought it was wholemeal wheat.
Having said that, it was back in the days before I got a meter and knew what grains (any grains) did to my blood glucose levels. Since then I have given up barley bread as well as the other options, since it was sending my blood glucose much too high.