This study primarily aimed to enhance the extraction of cutin from industrial tomato peel residues. Initially, the conventional extraction process was optimized using response surface methodology (RSM). Subsequently, high-pressure homogenization (HPH) was introduced to improve extraction efficiency and sustainability. The optimization process focused on determining the optimal conditions for conventional extraction via chemical hydrolysis, including temperature (100–130 °C), time (15–120 min), and NaOH concentration (1–3%). The optimized conditions, determined as 130 °C, 120 min, and 3% NaOH solution, yielded a maximum cutin extraction of 32.5%. Furthermore, the results indicated that applying HPH pre-treatment to tomato peels before alkaline hydrolysis significantly increased the cutin extraction yield, reaching 46.1%. This represents an approximately 42% increase compared to the conventional process. Importantly, HPH pre-treatment enabled cutin extraction under milder conditions using a 2% NaOH solution, reducing NaOH usage by 33%, while still achieving a substantial cutin yield of 45.6%. FT-IR analysis confirmed that cutin obtained via both conventional and HPH-assisted extraction exhibited similar chemical structures, indicating that the main chemical groups and structure of cutin remained unaltered by HPH treatment. Furthermore, cutin extracts from both conventional and HPH-assisted extraction demonstrated thermal stability up to approximately 200 °C, with less than 5% weight loss according to TGA analysis. These findings underscore the potential of HPH technology to significantly enhance cutin extraction yield from tomato peel residues while utilizing milder chemical hydrolysis conditions, thereby promoting a more sustainable and efficient cutin extraction process.