Selective recovery of recyclables is a major challenge when treating textile wastewater. For this reason, there is an urgent need to develop nanofiltration membranes with high permeability and selective filtration. In response, a novel composite PVDF loose nanofiltration membrane was developed by combining two different mixed amines system/dopamine (DA) followed by interfacial polymerization with benzoyl chloride (TMC). The two different amines systems were a mixture of GAZ and PEI and a mixture of PIP and PEI, respectively. The effects of GAZ/PEI and PIP/PEI on the microstructure was characterized by SEM, AFM, FTIR and XPS and performance of the membrane was also investigated. The effects of GAZ/PEI and PIP/PEI on the microstructure and the selective layer of membranes were different. The results stated that with the increase of GAZ/PEI the thickness of the selective layer, surface roughness decreased, while the fluxes of pure water and dye wastewater increased. However, with increasing PIP/PEI, surface nodules and roughness both increased. Contrarily, the thickness of the selective layer and PEG800 rejection first decreased and then increased, while the flux of pure water and the dye wastewater first increased and then decreased. The optimal GAZ/PEI and PIP/PEI were 9/91 and 50/50, respectively. When the GAZ/PEI was 9/91, the pure water flux and the RB5 wastewater flux were 20.7 L∙(m2∙h)−1 and 11.5 L∙(m2∙h)−1. The dye (RB5) retention rate was 94.3% and salt retention rate was 2.1%. However, when the PIP/PEI was 50/50, the pure water flux and RB5 wastewater flux were 26.6 L∙(m2∙h)−1 and 17.1 L∙(m2∙h)−1 increased by 87.3% and 134.2% respectively. The retention rates of RB5 and NaCl were 96.3% and 1.7%. The above results indicate that the composite PVDF LNF membranes prepared with mixed amine monomers instead of single amine monomers have good selective filtration performance.