(Being produced in vast quantity as one of by-product from cassava starch processing chains, cassava pulp has great potential for energy recovery by harnessing biogas through anaerobic digestion (AD). This study aims to enhance biogas production by comparative investigation in batch mode digestion. 5%TS w/v of cassava pulp mixed with mill effluent were pre-treated with 10 molar potassium hydroxide (KOH), sodium hydroxide (NaOH), and calcium hydroxide (Ca(OH)2) solution for 6 hours contact time. Effects of different alkaline pre-treatment on cassava substrate were assessed in total dissolved solid (TDS), soluble chemical oxygen demand (SCOD), Volatile Fatty Acids to Alkalinity ratio (VFA/TA), and reducing sugars. Daily accumulated biogas yield was taken as final indicator of the effect of different pre-treatment. KOH pre-treatment in pH 11 resulted highest dissolved solid 13.07 mg/L, and improved soluble chemical oxygen demand (SCOD) formation up to 75.61% (480,000 mg/L) than control substrate. The experiment revealed peak biogas production by KOH pre-treated substrate was found at day 6 after digestion executed, and achieved 546 ml. The finding proves out of different pre-treatment method applicable to cassava pulp, KOH pre-treatment could realistically increase biogas yield for cassava mills. Biogas production increased up to 101%, 92%, and 70% using KOH, Ca(OH)2 and NaOH respectively. However, when future provision to the technology for AD system and design is concerned, the choice of highly reactive alkali could lead to complication in the system.