While membrane technology emerges as one of the promising candidates for printing and dyeing wastewater treatment, it still suffers problems of “trade-off” effect and membrane fouling. It is therefore highly desired to fabricate high-performance membranes. This study reported a new functional polyvinylidene fluoride (PVDF)-Ni-Co membrane fabricated via an in-situ reduction method. The PVDF-Ni-Co membrane displayed conductive property, magnetic property and special in-situ micro-aeration function under assistance of electric field. Benefiting from in-situ micro-aeration function, the membrane showed excellent decoloration efficiency to Rhodamine B (RB), Congo red (CR) and methylene blue (MB) solutions. Particularly, the PVDF-Ni-Co membrane possessed 98.33% rejection to CR solution with flux up to 69.30 L m−2 h−1·bar−1, which is far better than the data reported in the literature. Moreover, in-situ micro-aeration was confirmed to be critical to enhance membrane antifouling performance. Cycling filtration results revealed that flux recovery rate (FRR) of PVDF-Ni-Co membrane reached to 90% and 94% for sodium alginate (SA) and bovine serum albumin (BSA) solutions, respectively. Thermodynamic calculation suggested that attractive energy of interaction between PVDF-Ni-Co membrane and foulants was largely reduced so that the foulants could hardly adhere onto membrane surface. This study simultaneously provided interesting findings regarding functional PVDF-Ni-Co membrane as well as its fabrication strategy, and new membrane fouling mitigation method of in-situ micro-aeration.