Mix all the herbs and spices (paprika, garlic, salt, pepper, cayenne, oregano, thyme) together in a small bowl.
Pat the pork dry with paper towels then rub HALF of the spice mix all over the pork.
Heat the oil in a large saute pan over medium-high heat.
Sear the pork until well browned on all sides, about 3 minutes per side, then transfer the seared pork to a large slow cooker and set aside.
Keep the pan over medium-high heat then add the diced onion, diced bell pepper, diced celery, vinegar, and remaining spice mix to the pan and cook, using a wooden spoon to stir and scrape the bottom of the pan to release any stuck on bits, until vegetables have softened a bit, about 5 minutes.
Transfer the contents of the pan into the slow cooker over top of the pork.
Place the lid on the slow cooker and cook on LOW until pork is pull apart tender, about 8 hours.
Use two forks to pull apart and shred the pork, discarding the bone.
Turn off the slow cooker and allow the pork to sit while you make the rice.
MAKE THE RICE:
Stir together the rice, water, and salt in a medium-size saucepan over medium-high heat and bring to a slight boil.
Place a lid on the pan and reduce the heat to low and simmer for 10 minutes, making sure to keep the lid on the entire time.
Turn off the heat and let the rice sit on the stove, still keeping the lid on, for 15 more minutes.
TO SERVE:
Fluff the rice with a fork and serve with the pulled pork and hot sauce on the side.
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