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Season the pork generously with salt and pepper. In a large fry pan over medium-high heat, warm the olive oil. Working in batches, add the pork and sear, turning as needed, until well browned on all sides, 6 to 7 minutes. Using a slotted spoon, transfer to a plate.
Pour off most of the fat from the pan and return it to medium-high heat. Add the onion and thyme and sauté until the onion is golden brown, about 5 minutes. Add the garlic and rosemary and cook for 1 minute. Pour in the wine and vinegar and stir to scrape up the browned bits from the pan bottom. Transfer the contents of the pan to a slow cooker. Add the broth and the pork and stir to combine. Cover and cook on low according to the manufacturer’s instructions for 5 to 6 hours, stirring 2 or 3 times during the first 2 hours. Stir in the kale, cover and cook for 30 to 60 minutes. The pork and kale should be very tender.
Using the slotted spoon, transfer the pork and kale to a platter. Skim any fat off the cooking liquid, then drizzle the liquid over the meat and serve immediately. Serves 6.
Adapted from Williams-Sonoma One Pot of the Day, by Kate McMillan (Weldon Owen, 2012).