Snakebite envenomation represents a significant global emergency health concern, necessitating rapid and accurate medical intervention. Accurate detection and identification of snake venom are essential not only for clinical diagnosis but also for ecological conservation efforts. In this study, we report the synthesis of a hydrogen-bonded organic framework-on-metal-organic framework (HOF-on-MOF) heterostructured material, engineered through the synergistic interactions of robust hydrogen bonds and pi-pi stacking forces. This material demonstrates unique dual enzyme-mimetic properties, exhibiting both highly peroxidase-like and laccase-like catalytic activities. By utilizing the carboxyl groups on the surface of HOF-on-MOF, we developed a biosensor (HOF-on-MOF-beta-BGT-apt) using an amino-modified beta-bungarotoxin aptamer (NH2-beta-BGT-apt) via amide bonding. Combining the dual enzyme-mimetic activity of the HOF-on-MOF composite material, we designed a colorimetric biosensor capable of dual-signal detection of beta-bungarotoxin (beta-BGT), enabling sensitive and intuitive detection with a low detection limit. The applicability of the colorimetric sensor for beta-BGT detection in human serum was assessed, highlighting its significant potential for biosensing and clinical diagnosis.