Citrate salts (CSs), as one type of organic salts, have been widely used in the food and pharmaceutical industries. Accurate and quantitative detection of CSs in food and medicine is very important for health and safety. In this study, an asymmetric double-opening ring metamaterial sensor is designed, fabricated, and used to detect citrate salts combined with THz spectroscopy. Factors that influence the sensitivity of the metamaterial sensor including the opening positions and the arrangement of the metal opening ring unit, the refraction index and the thickness of the analyte deposited on the metamaterial sensor were analyzed and discussed from electromagnetic simulations and THz spectroscopy measurements. Based on the high sensitivity of the metamaterial sensor to the refractive index of the analyte, six different citrate salt solutions with low concentrations were well identified. Therefore, THz spectroscopy combined with a metamaterials sensor can provide a new, rapid, and accurate detection of citrate salts.