Atmospheric pressure plasma polishing (APPP) method is a novel non-contact machining technology. It utilizes atmospheric pressure plasma to excite reactive radicals which cause chemical reactions with surface atoms to perform atom-scale removal process. Since the machining process is chemical in nature, APPP method avoids surface/subsurface defects. The removal process is a complicated integrated action which is affected by many factors, such as radio frequency power, gas ratio, temperature, and the like. Hence, it is necessary to monitor and analyze the process from different aspects and by various means. Through the analysis of atomic emission spectroscopy, the impacting rules of the radio frequency power and gas ratio were investigated. The temperature distribution on the workpiece surface was initially established by experiments and the results correspond well with the qualitative analysis conclusion from finite element method. Then, by initial technology optimization, the removal rate of 1.46mm3/min and Ra 0.6nm surface roughness were achieved in subsequent machining operations.