Advanced functionalities textiles embedding electronic fibers, yarns and fabrics are a demand for innovative smart cloths. Conductive electrospun membranes and yarns based on polyaniline/polyvinylpyrrolidone (PANI/PVP) were investigated using the chemical modification of PANI instead of using conventional coating processes as in-situ polymerization. PANI was synthesized from the aniline monomer and the influence of the oxidant-to-monomer ratio on electrical conductivity was studied. The optimized conductivity of pellets made with pressed PANI powders was 21 S·cm−1. Yarns were then prepared from the t-Boc-PANI/PVP electrospun membranes followed by PANI protonation to enhance their electrical properties. Using this methodology, electrospun membranes and yarns were produced with electrical conductivities of 1.7 × 10−2 and 4.1 × 10−4 S·cm−1.