Titanium dioxide (TiO2) material is suitable for sensing applications due to higher electron mobility, stability, high sensitivity to water vapor and more easily desorb physisorbed water molecules. However, the non-homogeneous formation of TiO2 nanotube arrays due to cracking structure is a common issue. Cracking during the preparation of TiO2 nanotube arrays (TiO2 NTAs) films can lead to the deterioration and malfunction of the nanotubes. The work presented here describes the niobium-doped TiO2 NTAs (Nb-doped TiO2 NTAs) films prepared by the dual-step electrochemical methods at different doping concentrations (1 to 7 at%). It was found that the film doped at 3 at% and annealed at 500 °C showed excellent conductivity with a value of 0.52 S. cm−1. Results showed that the TiO2 NTAs exhibited a humidity sensitivity of 239.85. The humidity sensing performance of the fabricated TiO2 NTAs has been enhanced to 602.15 by doping with 3 at% of Nb. The enlargement of the area facilitated a slight increment of humidity sensitivity of Nb-doped TiO2 NTAs films. This phenomenon was induced by reducing the average diameter of NTAs in TiO2 film when the Nb dopant occupied the TiO2 structure (59 to 48 nm). Nb is commonly combined with TiO2 material as its regarded as a promising dopant for modifying crystalline structure. The Nb-doped TiO2 NTAs shows high sensor stability since the Nb ions widen the host TiO2 lattice thus improving the conductivity of TiO2. The optimized Nb-doped TiO2 NTAs films using the electrochemical cathodization method shows it is applicable for humidity sensor.