Early warning sensors rapidly monitor critical temperatures, humidity, and fires, which are crucial to reduce or avoid natural disasters in complex environments, such as fire or water disasters. Here, a highly sensitive, readable, and dual‐functional sensor is designed for a fast‐response fire alarm and rapid humidity detection based on sustainable biological films (named MSCG films). The MSCG films are composed of grafted sisal nanofibers (MgC), silk nanofibers, graphene, and citric acid (CA). After crosslinking with CA, MSCG films exhibit good wet strength (i.e., 128.8 MPa) after soaking in 100 °C water, thus confirming that the films would be applicable to a broad temperature range in humid environments. After flame ignition, the MSCG films are rapidly carbonized to activate an alarm sound and a light in the circuit with a fire response time as short as 1 s. It exhibits ultrafast temperature response/recovery time (i.e., 0.1 s/0.3 s) and rapid humidity response time (i.e., 0.9 s). The dual‐functional sensor is further assembled into a versatile sensor system for real‐time monitoring of fire accidents and environmental humidity, which can be integrated into consumer electronics, such as portable laptops and mobile phones.