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In a large pot, combine the potatoes, 3 tablespoons salt, 2 tablespoons of the vinegar and 2 quarts water. Bring to a boil and cook, stirring, until a skewer inserted into the potatoes meets no resistance, about 25 minutes. Meanwhile, heat the oven to 500°F with a rack in the middle position. In a small bowl, stir together the mayonnaise, 2 tablespoons of the vinegar and ¼ teaspoon pepper; set aside.
Drain the potatoes, then transfer to a rimmed baking sheet and toss with the oil and 2 tablespoons of the vinegar. Using the bottom of a dry measuring cup, flatten each potato so it splits open but remains intact. Roast without stirring until well browned, 30 to 35 minutes.
Remove from the oven, drizzle the remaining 2 tablespoons vinegar over the potatoes and sprinkle with ½ teaspoon salt and ¼ teaspoon pepper. Using a wide metal spatula, scrape up the potatoes and toss to coat. Transfer to a platter and drizzle with half of the mayonnaise mixture. Sprinkle with chives and serve the remaining mayonnaise on the side.