The agro-food industries generate significant waste with adverse effects. However, these byproducts are rich in polyphenols with diverse bioactivities. Innovative non-thermal extraction (NTE) technologies (Naviglio extractor®, cold plasma (CP), high hydrostatic pressure (HHP), pulse-electric field (PEF), ultrasound-assisted extraction (UAE), etc.) and their combinative effect (integrated UAE + HPPE, integrated PEF + enzyme-assisted extraction, etc.) could improve polyphenolic extraction. Hence, this article comprehensively reviewed the mechanisms, applications, drawbacks, and safety assessment of emerging NTE technologies and their combinative effects in the last 5 years, emphasizing their efficacy in improving agro-byproduct polyphenols' extraction. According to the review, incorporating cutting-edge NTE might promote the extraction ofmore phenolic extractfrom agro-byproducts due to numerous benefits,such as increased extractability,preserved thermo-sensitive phenolics, and low energy consumption. The next five years should investigate combined novel NTE technologies as they increase extractability. Besides, more research must be done on extracting free and bound phenolics, phenolic acids, flavonoids, and lignans from agro by-products. Finally, the safety of the extraction technology on the polyphenolic extract needs a lot of studies (in vivo and in vitro), and their mechanisms need to be explored.