Langmuir-Blodgett (LB) films composed of DPPC and DNP-cap-DPPE phospholipids were characterized by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectrometry (SSIMS). These surface analytical techniques were systematically evaluated with respect to capabilities for the determination of film composition, orientation and thickness. Mixed monolayers were utilized to investigate quantitative compositional analysis capabilities. Orientation information was obtained using angle dependent XPS and by utilizing variations in the extent of Ag cationization of molecular ions in SSIMS of DPPC monolayers on Ag substrates. Film thickness determinations were provided by XPS studies of monolayer and multilayer DPPC films.