Slippery liquid-infused porous surfaces (SLIPS) – a new class of bio-inspired liquid-repellent surfaces – comprise arbitrarily porous architectures filled with oils that exhibit high interfacial tensions to probe liquids and present ultralow contact angle hysteresis (<〖10〗^°). However, before practical technologies based on SLIPS can be designed at large-scale, a number of fundamental questions remain to be answered. For instance, depending on the sign of the spreading coefficient of the Vapor(V)-lubricant oil(O)-liquid(L) system, defined as S_(OL(V))=γ_LV-γ_LO-γ_OV>0, the lubricating layer forms a layer at the liquid-vapor interface (here, γ_LV is a liquid-vapor interfacial tension, γ_LO – liquid-oil, and γ_OV – oil-vapor). This “cloaking” of liquid drops can deplete SLIPS’ lubricant over time and contaminate the probed liquid. So far, cloaking has been investigated by contact angle goniometry and confocal microscopy, which cannot resolve films of molecular thickness and factors that govern the equilibrium thickness of those films are not entirely clear. Here, we report on the development and application of a reflective-mode SFA platform to characterize the cloaking of water droplets placed on SLIPS. A multilayer matrix method is utilized to analyze the interferometry data. Using this complementary experimental and analytical approach, we determined the thickness of the cloaking layer for the FDTS(solid)-VF-40(lubricant)-water(probe liquid)-air system to be z3= 7±1 nm. Towards deeper insights into the intermolecular and surface forces responsible for cloaking, we demonstrate that repulsive van der Waals interactions are responsible for stabilizing the cloaking film at the water-air interface. Our experimental platform and the analytical framework should facilitate investigations of other SLIPS and probe liquid systems down to the molecular-scale resolution. These findings might aid the rational design of SLIPS, e.g., for drag reduction, anti-biofouling, and anti-corrosion. In addition to investigating SLIPS, We addressed the following questions with the help of atomic force microscopy (AFM): (i) how do zwitterionic osmolytes modulate electrostatic and hydrophobic interactions in nanoscale confinement, and (ii) is it possible to have two negatively charged surfaces attract each other? Our findings are presented as appendices in this thesis.