Preheat the oven to 400ºF and line a baking sheet with parchment paper. Peel the beets and carrots and remove the seeds from the pepper. Cut the beets into wedges. Chop the carrots and pepper into chunks.
Transfer the veg to the baking sheet and toss with the olive oil, salt and pepper. Bake the veggies for 35-40 minutes, turning halfway.
Meanwhile, rinse the barley, then add it to a medium saucepan along with 2-1/2 cups of water. Cover the pot and bring to a boil. Reduce the heat and simmer for about 20 minutes or until all the water has been absorbed. Give the barley a good rinse with cold water, drain it and set aside.