Sear the Chicken for Flavor: Begin by lightly coating your slow cooker insert with nonstick spray. In a large skillet, heat 1 tablespoon of olive oil over medium-high heat. Season both sides of the chicken with salt and pepper. Once the oil is hot and shimmering, place the chicken in the skillet in a single layer. Let it sear undisturbed for 3–4 minutes until golden brown, then flip and cook the other side for about 2 minutes. Transfer the browned chicken to the bottom of your slow cooker.
Sauté Aromatics for Depth: Lower the skillet heat to medium. Carefully wipe out any excess residue with a paper towel, then add the remaining 2 teaspoons of olive oil. When heated, add the chopped onion and cook for about 3 minutes, until slightly softened. Stir in the minced garlic and 1 tablespoon of balsamic vinegar, cooking for another 60 seconds until fragrant and slightly reduced. Scrape the mixture (including any flavorful bits stuck to the pan) into the slow cooker over the chicken.
Add Vegetables and Seasoning: Layer the crushed tomatoes, diced bell pepper, sliced mushrooms, and Italian seasoning over the chicken and sautéed aromatics in the slow cooker. Do not stir; keeping the chicken on the bottom allows it to absorb maximum flavor.
Slow Cook Until Tender: Cover and cook according to the type of chicken used:
Chicken Breasts: Cook on LOW for 4–5 hours or HIGH for 1½–2½ hours
Chicken Thighs: Cook on LOW for 5–6 hours or HIGH for 3–4 hours. The chicken is ready when it reaches an internal temperature of 165°F. At that point, transfer it to a plate and either shred, chop, or leave whole based on your preference.
Thicken Sauce for Better Texture (Optional but Recommended): If you have time, leave the slow cooker uncovered and turn it to HIGH for about 1 hour. This helps the tomato sauce reduce and intensify in flavor. Right before serving, stir in the remaining ½ teaspoon of balsamic vinegar to brighten the sauce. Taste and adjust seasoning with additional salt or pepper if needed.
Serve and Enjoy: Return the chopped or shredded chicken to the thickened sauce, or serve whole pieces topped with a generous spoonful of sauce. Plate over your base of choice—such as pasta, polenta, or veggie noodles—and finish with a sprinkle of fresh parsley and Parmesan.