Conducting electrospun fiber mats based on PLA and PAni blends were obtained with average diameter values between 87 and 1 006 nm with PAni quantities from 0 to 5.6 wt.-%. Structural characteristics of fiber mats were compared to cast films with the same amount of PAni and studied by SEM, SAXS, and AFM. Thermal properties of fiber mats and cast films were compared by DSC analyses. Mechanical properties of fiber mats were also evaluated. It was found that electrospinning process governs the crystal structure of the fibers and strongly affects fiber properties. New properties of PLA/PAni blends are reported due to the size fiber reduction.