Bring a pot of salted water to a boil. Add the barley; cook until tender, 45 to 50 minutes. Drain well and transfer to a large bowl.
Heat 2 tablespoons olive oil in a large skillet over medium-high heat. Add the zucchini and cook, stirring, until browned, 4 to 5 minutes. Add the corn and cook until just tender, 2 to 3 minutes. Season with 1/2 teaspoon salt and a few grinds of pepper. Add the vegetables to the barley and let cool.
Whisk the vinegar, the remaining 6 tablespoons olive oil, 1/4 teaspoon salt and a few grinds of pepper in a small bowl. Pour the dressing over the barley salad, add the scallions and basil and toss. Top with the goat cheese.