It is well known that nucleate boiling heat transfer and critical heat flux can be significantly enhanced by micro- and nano-scale structures of a boiling surface, which change the fundamental boiling parameters such as nucleation site density, dry area fraction and triple contact line density. In order to understand and model the physical mechanisms of the enhancements on a structured surface, it is required to measure such fundamental parameters. However, it is very challenging to detect the microscopic boiling parameters on structured surfaces using conventional measurement and visualization techniques for surface temperature and liquid-vapor phase distribution. In this study, a new visualization technique using infrared thermometry is presented to measure the microscopic boiling parameters on a boiling surface with micro- and nano-scale structures. The augmentations of boiling heat transfer coefficient and critical heat flux on the tested surfaces with different structures are interpreted with the change of microscopic boiling parameters.