Plasma Electrolytic Polishing (PEP) is an advanced anodic process that enhances stainless steel surfaces through controlled electrochemical dissolution and plasma-mediated modification. This study demonstrates that PEP treatment of AISI 304 SS at 300 V in aqueous urea solution (3.0 wt.%)/NH₄NO₃ (0.25 wt.%) achieves remarkable improvements: surface roughness decreases by 54.6% (from 0.197 ± 0.023 μm to 0.0895 ± 0.0205 μm) with minimal mass loss (0.0035 g·cm⁻²) in just 20 min. Tafel analysis showed a 99% reduction in corrosion rate (0.00497 mm yr⁻¹) compared to untreated AISI 304 SS (0.094 mm yr⁻¹). Cyclic Potentiodynamic Polarization (CPDP) measurements indicated superior pitting resistance (E_pit = +0.423 vs. +0.486 V for PEP processing). XPS analysis elucidates the underlying mechanisms, showing a 91% increase in the Cr/Fe ratio (0.44 to 0.84) and complete transformation of surface oxides to protective Cr₂O₃ (57.34 wt.%) and Fe₃O₄ (55.88 wt.%), which collectively explain the enhanced corrosion resistance.