Anaerobic digestion (AD) has undergone many developments since its first appearance. Despite that, there are still some environmental and economical obstacles that are limiting its sustainability. On the other hand, different types of starch have proven their effectiveness in some different applications. Food processing industries are considered one of the largest generators of waste in the environment. With an aid of the response surface methodology (RSM), the proposed study aimed to find an optimised way to overcome the obstacles by studying the impacts of the starch isolated from the potato peels on the biogas produced from the AD of potato peels before and after starch separation. The study found that potato peels represented approximately 12.5% of the potato total weight. The starch has only a slight influence on the quantity of the biogas produced and much lower influences on its quality. This finding suggests further investigation is required on the production of starch bio-based products simultaneously with the biogas and bio-slurry, which may mitigate environmental influences and economical obstacles of AD and make it more commercially attractive. The study showed also that the highest energy gain by the g-VS/0.2 L of potato peels was 62.9% at 35 °C, 1.62 g-VS/0.2 L organic concentration and 50% sludge concentration, which yielded a maximum CH4 of 72.4%.