Wastewater reclamation possesses great potential to synchronously solve water pollution and water scarcity problems. However, the established reclamation technologies commonly suffer from high energy consumption and intricate operation, which hinder their widespread applications. The current study proposed a novel capacitive-deionization (CDI)-based process which achieved a simultaneous removal of salinity and organic matters in wastewater. Two novel types of composite electrodes with a dual-layer configuration were fabricated on the basis of an in-situ combination approach. Carbon nanotube (CNT) and activated carbon were separately used to prepare the conductive supporting layer, and polyvinylidene fluoride (PVDF) was used to fabricate the membrane selective layer. Desalination behaviors of the resultant CNT/PVDF and carbon/PVDF electrodes were systematically investigated using a lab-built electrically-enhanced desalination-filtration (EEDF) system. Various model solutions were prepared using inorganic substrates, sodium alginate (SA), bovine serum albumin (BSA), and humic acid (HA) to evaluate the desalination performance of different electrodes. Consequently, the casting solution containing 17% (w/w) PVDF was selected as the optimum recipe for the membrane layer. Compared with the CNT layer, the carbon layer exhibited a better desalination performance, indicating a better alternative for composite electrode fabrication. Desalination behaviors in the cross-flow and penetration modes of the EEDF system were compared. As a result, the penetration mode was found to be more favorable to deionization. Moreover, the selective PVDF layer not only dramatically enhanced the selectivity by similar to 60% but also potentially endowed the electrode with antifouling features, suggesting promising applications in wastewater reclamation areas.