How to Make It
Preheat oven to 425°F. Season chicken with pepper and ¾ teaspoon of the salt.
Heat oil in a large ovenproof skillet. Working in 2 batches, add chicken thighs, skin side down. Cook, flipping once, until chicken is deeply browned and crisp, 5 to 6 minutes per side. Transfer to a plate. Repeat with remaining chicken thighs.
Add broth, barley, 1 tablespoon of the thyme, and remaining ¼ teaspoon salt to skillet, stirring to submerge all barley. Bring to a boil. Return chicken to skillet, skin side up. Transfer to oven and bake until chicken is cooked through and barley is tender, 10 to 12 minutes.
Transfer chicken to a plate and stir peas into barley. Return skillet to oven and cook until peas are bright green and tender, about 3 minutes.
Serve chicken over barley, topped with remaining 1 tablespoon thyme.