A novel sensor architecture based on thin film of tapioca decorated within nitrogen‐doped titanium dioxide (N‐TiO2) nanoparticles is reported. The nanostructures were characterized by scanning electron microscope, transmission electron microscope, X‐rays diffraction and voltammetric techniques. The proposed electrode was used for detection of low concentrations of 17‐β estradiol in without purification step, which was investigated by using linear sweep adsorptive stripping voltammetry. Under optimal conditions, the analytical curve was linear over a 17β‐estradiol concentration range of 9.9×10−6 to 1.4×10−5 mol L−1, with a detection limit of 1.7×10−7 mol L−1. The tapioca and N‐TiO2 nanoparticles homogeneous film was applied for detection of 17‐β‐estradiol in tap water and synthetic urine samples, which presented satisfactory results.