The support substrates were modified with the aqueous solutions of 1 and 3 wt% of polyvinyl pyrrolidine (PVP) as intermediate buffer layer followed by NaA zeolite seed (prepared hydrothermally at 85 °C for 2 h) coating with 2.5 wt% aqueous dispersion in each case. A better surface coverage with the oriented layer of NaA seed crystals was found with 1 wt% PVP buffer layer. The secondary crystallization of NaA membranes in the PVP-seed-coated supports was carried out hydrothermally at 65 °C for 2, 4, 6 h (single-stage each) and (2 + 2), (4 + 2)h (double-stage each) crystal growth processes. The crystallization behaviours of NaA membranes were studied by X-ray diffraction (XRD) while the microstructures of the same films were observed by scanning electron microscope (SEM). The single-stage secondary crystallization at 65 °C for 4 h showed highly interlocked and oriented NaA grains in the membranes and it rendered the permeance value of 2.2 × 10−8 mol m−2s−1Pa−1 for single gas, nitrogen (N2) at ambient temperature (30 °C).