In contrast with the conventional ceramic/oxide humidity sensors (HSs), a self-powered piezoelectric biopolymer HS with reasonable sensitivity, reliability, and a nontoxic and eco-friendly nature is highly desirable. A piezoelectric nanogenerator (PNG)-driven biopolymer-based HS provides a pathway toward a sustainable and greener environment in the field of smart sensors. For that, a piezoelectric collagen nanofibril biopolymer coated on to a cotton fabric has dual functionality (energy harvesting and sensor). Collagen PNG generates a maximum of 45 V/250 nA upon 5 N and can also work as a sensor to measure various percentages of relative humidity (% RH). The HS shows a linear response with a good sensitivity (0.1287 μA/% RH) in the range of 50-90% RH. These results open a field of eco-friendly multifunctional nanomaterials toward the development of noninvasive, implantable smart bio-medical systems. © Copyright 2018 American Chemical Society.