In this paper, we used automated 15N 13C analysis MS (ANCA-MS) and stable carbon isotope ratio analysis to analyze samples of rice- and cane molasses-based spirits and their constituent principal ingredients. This methodology was developed to distinguish, in a scientifically accurate manner, rice spirits made of rice from that made of cane molasses. Spirits with different mixed ratios of rice and cane molasses were also prepared for a detection capability test. Series dilution for spirit samples was performed to assess operational consistency. Test results demonstrated that 13C/12C values, as measured by ANCA-MS, can be used as reliable benchmark to distinguish between the two types of rice spirits. It is recommended that test samples should be distillated or diluted to an equivalent level of ethanol prior to measuring 13C/12C values. Data established in this paper can provide criteria necessary to monitor rice spirits sold in the marketplace.