In this work, biochar-based humidity sensors were prepared by drop-coating technique. Polyvinylpyrrolidone (PVP) was added as an organic binder to improve the adhesion of the sensing material onto ceramic substrates having platinum electrodes. Two biochars obtained from different precursors were used. The sensors were tested toward relative humidity (RH) at room temperature and showed a response starting around 5 RH%, varying the impedance of 2 orders of magnitude after exposure to almost 100% relative humidity. In both cases, biochar materials are behaving as p-type semiconductors under low amounts of humidity. On the contrary, for higher RH values, the impedance decreased due to water molecules adsorption. When PVP is added to SWP700 biochar, n-p heterojunctions are formed between the two semiconductors, leading to a higher sensitivity at low RH values for the sensors SWP700-10% PVP and SWP700-20% PVP with respect to pure SWP700 sensor. Finally, response and recovery times were both reasonably fast (in the order of 1 min).