The bio-functional properties of olive oil products and by-products rely greatly on the proportions and types of the endogenous phenolics that may favorably/unfavorably change during various processing conditions. The olive oil industrial activities typically produce (i) olive oils, the main/marketable products, and (ii) olive mill by-products. The mechanical processing of olive oil extraction is making progress in some areas. However, the challenges inherent in the existing system, taking into consideration, the susceptibilities of phenolics and their biosynthetic variations during processing, hamper efforts to ascertain an ideal approach. The proposed innovative means, such as inclusion of emerging technologies in extraction system, show potential for sustainable development of olive oil processing. Another crucial factor, together with the technological advancements of olive oil extraction, is the valorization of olive mill by-products that are presently underused while having great potential for extended/high-value applications. A sustainable re-utilization of these valuable by-products helps contribute to (i) food and nutrition security and (ii) economic and environmental sustainability. This review discusses typical processing factors responsible for the fate of endogenous phenolics in olive oil products/by-products and provides an overview of the possibilities for the sustainable processing to (i) produce phenolic-rich olive oil and (ii) optimally valorize the by-products.