The development of high performance membrane is crucial for enhanced separation efficiency of nanofiltration process in treating wastewaters from dye and textile industries. In this work, a novel thin-film composite nanofiltration membrane with an asymmetric separation layer composed of relatively compact skin and loose body was designed and fabricated for improved perm-selectivity and antifouling property. Nascent composite membrane with loose poly(piperazine amide) (PA) separation layer was interfacially synthesized and performed with secondary surface reaction using an aqueous tannic acid (TA) solution. Membrane characterizations verified the formation of compact TA skin on top of the loose PA layer through forming covalent bonds via esterification reaction. Compared with the composite nanofiltration membrane with PA symmetric separation layer having the same glucose rejection of about 82.0%, the permeability to pure water of the composite membrane with PA/TA asymmetric separation layer was higher by 28.0%, the water fluxes to aqueous solutions dissolved with model anionic dyes of alizarin yellow R, sunset yellow and Congo red under steady state were higher by 50.3, 43.9 and 36.1%, and the steady-state flux declines were lowered by 27.8, 43.4 and 23.5%, respectively. Furthermore, the PA/TA-based membrane also exhibited better antifouling property and rejection ability to alizarin yellow R.