Our earlier research prepared ferroelectric poly(vinylidene fluoride) (PVDF) homopolymer monolayers at the air-water interface using amphiphilic poly(N-dodecylacrylamide) (pDDA) nanosheets with Langmuir-Blodgett (LB) technique. However, the miscibility of solvent for PVDF with the water sub-phase in the Langmuir trough makes the film composition unclear in spite of the feeDing ratio of PVDF : pDDA (50 : 1). In this study, angleresolved X-ray photoelectron spectroscopy (AR-XPS) was used to investigate the surface chemical composition and the depth profile of the PVDF/pDDA LB nanofilms. The X-ray photoelectron spectroscopy (XPS) spectra confirmed by the detection of fluorine atoms that PVDF molecules were deposited successfully onto the substrate. The constant chemical composition with increasing takeoff angle from 15 to 75 reflects a well-regular layer structure of the PVDF LB nanofilm. The mixing ratio of PVDF : pDDA is 33 : 1, which contributes 89.8 wt% PVDF and 10.2 wt% in the PVDF/pDDA LB nanofilms.