The cathode/anode-electrolyte interfaces in lithium/sodium ion batteries act as the “gate” for the ion exchange between the solid electrode and liquid electrolyte. Understanding the interfacial properties of these solid-liquid interfaces is essential for better design high-performance lithium/sodium ion batteries. Here, we provide a novel method for studying solid-liquid interfacial properties of battery materials through combining physical vapor deposition (PVD) and beam-exit cross-sectional polishing (BEXP) followed by controlled environment multifunctional Scanning Probe Microscope (SPM). In this method, commercial battery materials can be either directly grown on the current collector substrates, or polished by obliqued Ar-ion beams to get a nanoscale flat surface which allows the multifunctional SPM to study sample directly in the liquid electrolyte or in protective oxygen/H2O free environment. This approach allows to investigate wide range of interfacial properties, including surface morphology, internal cracks, mechanical properties, electronic/ionic conductivity and surface potential, with nanoscale resolution in-operando during the battery cycles as well as post-mortem. • PVD and novel BEXP methods were introduced to prepare battery powder materials as perfect specimens for nanoscale SPM characterization. • Various physical/chemical properties of battery materials can be probed on the as-prepared specimens under liquid electrolyte using in situ/operando SPM techniques. • Ex situ/post-mortem analyses based on the controlled environment multifunction SPM characterizations can be achieved in the BEXP polished degradation battery electrodes. © 2021 The Authors