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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.
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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 sea salt and freshly ground pepper to taste. Add the vegetables to the barley and let it cool.
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Whisk the vinegar, the remaining 6 tablespoons of 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, walnuts and basil and toss.