Protective footwear for occupational use conducts static electricity through the upper, linings, insole and outsole into the ground. Footwear must be made from appropriate material to reduce the possibility of electrocution and other electricity-related incidents. In this study the influence of footwear materials for the upper and lining components’ structure on their electrical properties was investigated. For investigations leather and various textile laminates were chosen. The thickness of leather coating, composition of textile laminates, the upper-lining system, and relative humidity of the environment on electrical resistivity changes were evaluated. Leather shows antistatic properties at standard humidity, but its electrical conductivity greatly increases at high humidity due to the presence of polar groups in the leather structure. Textile lining laminates composed of natural and synthetic fibres are insulators, but their systems with leather at high humidity show resistivity values close to antistatic materials. Leather acrylic coating decreases the electrical conductivity of materials.