This study aimed to develop an efficient method for the extraction of bioactive compounds from green tea waste (GTW) toward its potential application in the food industry. GTW, which is generated during the harvesting and processing of green tea products, accounts for a global annual loss of nearly 1 million tonnes. Notably, this waste is rich in polyphenolic compounds, particularly catechins, which are renowned for their significant health benefits. We assessed the optimization of catechin extraction from GTW employing hot water extraction (HWE), ultrasound-assisted extraction (UAE), and ethanol extraction (EthE) techniques at different sample-to-solvent ratios (1:100, 1:50, and 1:20 w/v). The extraction temperature was set at 80°C for both HWE and UAE; however, for EthE, the temperature was slightly lower at 70°C, adhering to the boiling point of ethanol. High-performance liquid chromatography was used to determine the extraction efficiency by quantifying various catechins (i.e., catechin, epicatechin [EC], epicatechin gallate [ECG], epigallocatechin [EGC], and epigallocatechin gallate [EGCG]). In terms of the concentration for individual catechins, EC was found to be the highest concentration detected, ranging from 30.58 ± 1.17 to 37.95 ± 0.84 mg/L in all extraction techniques and ratios of solvents, followed by EGCG (9.71 ± 1.40-20.99 ± 1.11 mg/L), EGC + C (7.95 ± 0.66-12.58 ± 0.56 mg/L), and ECG (1.85 ± 0.71-6.05 ± 0.06 mg/L). The findings of DPPH (2,2-diphenyl-1-picryl-hydrazyl) free radical assay illustrated that HWE demonstrated the highest extraction efficiency at all ratios, ranging from 61.41 ± 1.00 to 70.36 ± 1.47 mg/L. The 1:50 ratio exhibited the highest extraction yield (25.98% ± 0.75%) compared to UAE (24.16% ± 0.95%) and EthE (22.59% ± 0.26%). Moreover, this method of extraction (i.e., HWE) produced the highest total catechins and %DPPH reduction. Consequently, HWE was the most efficient method for extracting catechins from GTW, underscoring its potential for valorizing waste within the food manufacturing industry.