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Remove ribs and stems from chard leaves. Cut in half, lengthwise, then slice crosswise into 2" pieces; set aside. Tear leaves into large pieces; set aside.
Combine vinegar, hot sauce, and brown sugar in small bowl, stirring until sugar is dissolved. Set aside.
Heat oil in large pot over medium. Add red onions and cook 5–8 minutes, stirring occasionally, until softened. Add garlic and reserved chard stems; season with sea salt and pepper. Cook 7–10 minutes, stirring occasionally, until stems are crisp-tender. Add reserved chard leaves, a handful at a time, letting them wilt slightly before adding more. Add sauce, stir to coat, and continue to cook until completely wilted. Season with sea salt and pepper, if needed.