Abstract The production of biofuel from waste has become an important topic for waste management and reducing its environmental hazard. Tea factory waste is a strong candidate due to its availability and sourceability. This study aimed to reveal the biochemical methane potential (BMP) of tea factory waste (TFW) and spent tea waste (STW). Additionally, the results revealed that both substrates had high biodegradability due to high VS removal. The BMP tests took 49 days under mesophilic conditions with a batch reactor and the cumulative methane yields were 249 ± 3, and 261 ± 8 mL CH4/g VS for TFW and STW, respectively. According to prediction data with the selected ANN model, which was 50 hidden layer sizes, trained with Bayesian Regularization algorithm, the maximum cumulative specific methane yield of the co-digestion was simulated as 468.43 mL CH4/g VS when the ratio of 65 and 35% (w/w by VS) of TFW and STW, respectively. The predicted methane yield for co-substrates was 183% higher than mono substrates. This result revealed that TFW can be a good candidate for biogas production as biofuel for not only its availability and sourceability but also the synergistic effect possible for co-digestion.