The present paper reports successful preparation of one-amide thin films from Nylon-6 granules, despite the fact that the shaping process of Nylon-6 has been considered technically difficult in nanoscale thus far. A molecular beam epitaxy apparatus was used for physical vapor deposition (PVD). The obtained thin film was studied by Raman spectra and X-ray diffraction analysis, and the results were compared with those for the Nylon-6 granules used as the PVD source. It was found that the main structures were similar, but the γ phase of Nylon-6 has only been observed in the deposited film. By changing the deposition time, a variety of thicknesses ranging from 20 to 100 nm was obtained. These were studied by X-ray reflectivity analysis and scanning probe microscopy. It was noted that the deposition rate strongly influences the quality of the thin film. The temperature-stability of deposited amide thin film was investigated by in operando Xray reflectivity measurement. During the temperature scan from 10 to 70 °C under ambient conditions, the greatest thickness reduction of 1.7% occurred when the temperature was below 28 °C. Above 28 °C, there was no clear change in the coefficient of thermal expansion, although the glass transition of Nylon-6 bulk can occur around 47 °C. Moisture control experiments revealed that some swelling can occur in the amorphous region in the deposited amide thin film. It is inferred that the reduction in molecular weight and γ crystalline form both contributed to the mobility of the molecules in the deposited amide thin film.