<p>The present work studied the Alternating Current (AC) responses and Humidity sensing studies for Lithium sulphate (Li₂SO₄)-doped Polyaniline (PANI) composites. Pure PANI was synthesized using the In-Situ polymerization method. The PANI/Li₂SO₄ (PLS) Composites were prepared by mixing chemically synthesized PANI with Li₂SO₄ in a vibration mill. The samples were structurally and morphologically characterized by XRD, FTIR, SEM, EDX, BET, TEM, and SAED patterns. An increase in the AC conductivity (σ _ac) of composites was 1.32 × 10^–2 S cm⁻¹ at 1&#xa0;MHz frequency for [0.90:0.10 wt%] of the PLS-5 composite. The conductivity increases in composites, compared to PANI and Li₂SO₄, observed and discussed based on the electron–hole exchange mechanism. The Humidity sensing studies are carried out for the PLS composites. The PLS composite samples show a drastic change in the resistance with % relative humidity (% RH). The sensing response, humidity hysteresis, Stability, and timing behaviours are recorded for the samples. The PLS-5 sample recorded a maximum change in resistance and showed a good sensing response. The mechanism for the sensing has been discussed based on the formation of the superficial layers.</p>