Bell peppers (Capsicum annuum L.) in various stages of maturity are widely used in the diets of individuals and in the food industry; they are consumed both fresh and after thermal processing. However, every type of processing impacts the overall textural and bioactive characteristics of this plant-based food. In order to quantify the changes in the bioactive substances and color-structural characteristics that occur during selected heat treatments (contact grilling, roasting, roasting combined with microwaving, and steam cooking) of bell peppers at three maturity stages (green, yellow, and red), analyses of antioxidant activity, reducing sugar content, polyphenolic compound content, textural properties, and color coordinates in the L*a*b* system were carried out. Some of the processes used, such as contact grilling (15.43 mg GAE/g d.b.) and roasting combined with microwaving (15.24 mg GAE/g d.b.), proved to be beneficial as the total polyphenol content of green peppers (2.75 mg GAE/g d.b.) increased. The roasting (3.49 mg TE/g d.b.) and steaming (6.45 mg TE/g d.b.) methods decreased the antioxidant activity of yellow bell peppers (14.29 mg TE/g d.b.). Meanwhile, the roasting (0.88 mg Glc/g d.b.), contact-grilling (2.19 mg Glc/g d.b.), simultaneous microwaving and roasting (0.66 mg Glc/g d.b.), and steaming (1.30 mg Glc/g d.b.) methods significantly reduced the content of reducing sugars and reducing substances in red bell peppers (4.41 mg Glc/g d.b.). The studies proved that in order to preserve the antioxidant and bioactive properties of bell peppers, it is necessary to consider the use of appropriately selected heat treatments, depending on the different stages of maturity. The proper selection of adequate thermal treatment can not only increase digestibility, but also improve the bioavailability of bioactive substances from this raw material.