Silicon carbide particle reinforced aluminum matrix composites (SiCp/Al), combine the properties of aluminum matrix materials and reinforced silicon carbide (SiC) particles, finding widespread application in aerospace, optics, and electronics. The increased hardness and electrochemical inertness of SiC particles present significant challenges in their processing. This research investigates the impact of photocatalytic processes on machining accuracy in electrochemical processing (ECM). The dissolution characteristics of SiCp/Al during ECM and photocatalytic-assisted electrochemical machining (PAECM) were analyzed with varying electrolyte compositions, using polarization curves and oxidation-reduction potential (ORP). Validation of improved machining accuracy in PAECM was achieved through no-feeding machining. PAECM, with its photocatalytic reactions, effectively blocked stray currents and stray corrosion, enhancing accuracy in profile creation. Comparative analysis revealed that PAECM exhibited smoother profiles and reduced Overcut Ratio (OCR) in hole and groove machining compared to ECM, particularly in groove machining. Adjusting machining gaps and reducing abrasive particle size in PAECM influenced groove depth and width, achieving optimal morphology with a 0.4 mm gap and a 2-3 nm abrasive particle size, resulting in a 370 μm depth.