Spent black tea (SBT) is a residue from tea beverage production and considered as a potential source of active polyphenols. This study aimed to develop a pilot-scale process on semi-continuous subcritical solvent extraction (SSE) of polyphenols from SBT by exploiting the lab-scale knowledge. Treatment of SBT with ethanol-water (50% w/w) as solvent at 125 °C and 0.3 MPa achieved a significantly higher yield of polyphenols (80.82 g gallic acid equivalents/kg black tea) with antioxidant activity (64.20 g gallic acid equivalents/kg black tea), compared to hot water extraction (HWE). SSE increased the soluble matter content in extracts than HWE. Based on the results of LC-MS, theaflavin-3,3′-digallate was the most abundant polyphenol from a total of 12 compounds to be extracted by SBT with 50% ethanol. The results suggested that SSE can be used as a scale-up extraction method to recover polyphenols from SBT.