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Slice potatoes in half lengthwise, then, if necessary, in half crosswise into 3-inch pieces. Toss in 2 tablespoon extra-virgin olive oil, 1/2 teaspoon salt and 1/4 teaspoon pepper. Roast on a rimmed baking sheet at 400°F for 20 minutes.
Meanwhile, prepare vinaigrette: In a large bowl, whisk 2 tablespoon extra-virgin olive oil, white wine vinegar, mustard, 1/4 teaspoon salt and 1/8 teaspoon pepper. Stir in chives. Toss hot potatoes in vinaigrette and serve warm.