Microplastics, particularly polyethylene terephthalate (PET) and polypropylene (PP) in both high- and low-density forms, represent persistent pollutants of growing concern in aquatic environments. This research develops a sustainable and integrated electrocoagulation–flotation (ECF) with ultrasound-assisted agitation to enhance the destabilization, aggregation, and separation of MPs from water. The hybrid ECF–ultrasound process improves charge neutralization, mitigates electrode passivation, and promotes energy-efficient particle recovery through enhanced bubble generation and flotation. To ensure complete remediation, a persulfate-based advanced oxidation process is incorporated as a post-treatment stage to degrade residual plastic waste after separation. Laboratory-scale experiments optimized using Response Surface Methodology demonstrate removal efficiencies exceeding 90% under optimal pH, current density, and treatment time. Characterization analyses using FTIR, SEM, and XRD confirm significant physical and chemical transformations after treatment. FTIR spectra show a reduction in characteristic PET and PP absorption peaks, indicating surface oxidation and partial polymer degradation. SEM micrographs reveal that microplastic particles become entrapped within dense aluminium hydroxide flocs, demonstrating effective aggregation and flotation. XRD patterns display a slight decrease in crystallinity, supporting the occurrence of structural modification during the hybrid process. The study also employs real-world plastic materials, such as beverage bottles and disposable plastic containers, to evaluate the practical performance of the system.