The interest in studying the electrical properties of WO3 center dot H2O powders is made absolutely necessary because their infrared modulation properties depend on their morphologies and electronic populations. Broadband dielectric and resistivity spectra of WO3 center dot H2O powders were recorded in a frequency range of 10(3)-10(10) Hz at temperatures varying between 200 and 300 K. Complex resistivity and permittivity diagrams have permitted thermal behavior of both dc-conductivity and permittivity to be obtained. A dielectric relaxation is found, attributed to water molecules motions. The role of the powder morphology has been investigated on two types of compounds: the first one being constituted by nanometric particles and the second by micrometric particles. Strong differences are observed in the thermal behaviors of the dc-conductivities (activation energies). Particle size effect is evidenced, giving rise to stronger electron localization on the nanometric particles. The permittivity values and the dynamical behavior of the structural water are also influenced by the particle size effect. A strong interaction between moving polarons and water molecules has been determined.