Prepare barley according to package instructions; set aside.
Heat a large cast iron or similar sturdy bottomed skillet, over medium heat, for 4 minutes.
Add the olive oil; as soon as the oil is hot and shining, but before it starts smoking, swirl to coat the pan.
Add the Brussels sprouts; shake the skillet a little and prod them so that an many as possible are cut-side down; use thongs to turn sprouts cut-side down, if necessary.
Let the sprouts sit, undisturbed for 5 to 8 minutes or until they develop a dark, caramelized sear.
Season with salt and pepper.
Continue cooking, about 6 to 8 minutes, stirring every few minutes, until the Brussels sprouts are browned all over and just turning tender.
Add balsamic vinegar and maple syrup.
Stir to coat and remove from heat.
While still hot, add barley, cranberries, and pecans to the skillet; toss to combine.
Top with gorgonzola.
