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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 a 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.