Pervaporation (PV) shows significant potential for the highly selective isopropanol (IPA). The pursuit of developing PV membranes with outstanding separation effect and enduring high purity permeation is an indispensable goal. Based on polyamide (PA) separation layers, a polydopamine (PDA) mixed g-C3N4 quantum dots (gCNQDs) coating as the interlayer was deposited onto a porous ceramic hollow fiber substrate to fabricate thin-film nanocomposite membranes with an interlayer (TFNi). The nanocomposite interlayer enabled the formation of a smoother and highly separated selective polyamide layer. The separation factor exhibited a 31-fold enhancement with the augmentation of the blending fraction of gCNQDs during the PDA coating process. The resulting TFNi membrane attained an exceedingly high separation factor of 10270 ± 90 with a permeate water concentration of 99.9% and demonstrated a satisfactory flux of 1.40 ± 0.08 kg⋅m-2⋅h-1 during the PV process of 90 wt% IPA dehydration at 60 °C. This study presents a fresh perspective on the implementation of nanocomposite interlayers, which is expected to expand the application of high-performance TFNi membranes in PV dehydration processes.