biomacromolecule remains a challenge. [ 11 ] Diffi culties associated with the extraction of natural melanin have inspired the development of synthetic melanin, [ 12 ] which can mimic the properties of natural melanin, including its hydrationdependent conducting behavior. For example, the conductivity of 1 mm thick 3,4-dihydroxyphenylalanine (DOPA) melanin pellets was found to be 10 −13 S cm −1 at relative humidity (RH) of 0% and 10 −5 S cm −1 at 100% RH, an eight order of magnitude difference. [ 13 ] Thin fi lms are considered ideal building blocks for constructing miniatured sensing devices due to high surface to volume ratio. However, the preparation of homogeneous melanin thin fi lms at a large scale are extremely diffi cult using conventional solution processing methods due to insolubility of natural and synthetic melanin. [ 6 ] Several attempts have been made to prepare DOPA melanin thin fi lms. For example, ready-made DOPA melanin powders have been used to prepare ammonia-aided melanin aqueous dispersions, which was used to produce DOPA melanin fi lms at a micrometer scale by spin casting. [ 6 ] Synthesized DOPA melanin, soluble in organic solvents such as dimethyl sulfoxide (DMSO) and N , N -dimethyl formamide was also used to produce nanofi lms using spin coating. [ 14 ] A 30 nm thick DOPA melanin nanofi lm spin coated on silicon from DMSO suspension showed about a three order of magnitude change in conductivity on going from 50% RH to 100% RH. [ 15 ] The adhesive proteins secreted by mussels have inspired the design of dopamine-melanin nanofi lms dozens of nanometers thick. [ 16 ] Previous studies have focused mainly on hydration dependence of melanin conductivity (humidity sensitivity), without assessing other parameters critical for practical applications of humidity sensors including response and recovery times, and humidity detection range.This study describes a highly sensitive humidity sensor with rapid response fabricated of self-assembled dopamine-melanin thin fi lms that formed at air/solution interface. These thin fi lms could be transferred to a variety of substrates. Film thickness could be controlled in the nanoscale range by adjusting the reaction times between dopamine monomers and melanin. Examination of the fi lm surface morphology using atomic force microscopy (AFM) showed that the surface was compact and smooth at the nanoscale level. These dopamine-melanin thin fi lm sensor exhibited ultrasensitive and rapid responses to moisture, relatively good reproducibility, and its linear response to RH, allowing their calibration.Dopamine undergoes oxidative polymerization in aqueous solutions in the presence of dissolved oxygen, resulting insoluble melanin aggregates. [ 16 ] In practice, the synthesis of dopamine-melanin starts with deprotonating protonated dopamine (e.g., dopamine hydrochloride), which is chemically stable in air. High-quality melanin thin fi lms were formed at