Because food byproducts (waste) are rich in phytoconstituents, valorizing them is crucial for global food security. However, conventional extraction (CE), including decoction, maceration, Soxhlet, etc., for agro byproducts' polyphenol extraction are time-consuming and rely significantly on vast volumes of potentially aggressive solvents. Hence, Avantgarde extraction technologies, including non-thermal (high hydrostatic pressure (HHPE), pulsed-electric field (PEF), high voltage electrical discharges (HVED), etc.) and thermal extraction (supercritical fluid (SCF), subcritical water extraction (SWE), microwave-assisted extraction (MAE), etc.), as well as their thermal combinations (SCF-PLE, SCCO2-SWE, SCCO2-MAE, etc.), non-thermal combinations (HHPE + UAE, PEF + UAE, HVED + UAE, etc.) and combined thermalnon-thermal (MAE-UAE, etc.) are increasingly replacing CE. However, a review of combined Avant-garde extraction escalation technologies (non-thermal/thermal extraction matrix) for extracting polyphenols from agro-byproducts is limited. Hence, this manuscript reviewed Avant-garde extraction technologies (non-thermal/thermal extraction matrix) for extracting phenolics from agro-byproducts in the last 5 years. The key factors affecting polyphenols' extraction from the byproduct, the recent applications of Avant-garde technologies, and their principle were reviewed using databases from Web of Science and Lens.org. The results demonstrated that combined Avant-garde extraction escalation technologies increase extractability, resulting in polyphenols with higher extraction rates, fewer contaminants, and preservation of thermosensitive components. Therefore, combined Avant-garde extraction technologies should be explored over the next five years. Implementing an integrated process and the strategic sequencing of diverse Avant-garde extraction technologies are important. Thus, further investigation is required to explore the sequencing process and its potential impact on the extraction of phenolics from agro-byproducts.