Citrus fruits are susceptible to microbial infection during storage and transportation, leading to weight loss, quality deterioration and even physiological decay. In this study, a layer-by-layer (LbL) self-assembly edible coating based on chitosan and Sodium carboxymethyl cellulose (CMC) was prepared using electrostatic deposition. Postharvest citrus fruits (Citrus reticulate cv. ‘Chunxiang’) were coated either with the LbL coating, which exhibited an increased transmission rate of water vapor, or with single chitosan coating. The data of some physiological indexes of citrus coated with LbL coating and single coating were compared after being stored at 13 ± 2 °C and at relative humidity (RH) at 80–85% (shelf-life condition) for 10 days. Results demonstrated that the LbL deposited coating was effective at maintaining morphological and microstructural attributes, increasing the surface brightness, firmness and the content of titratable acid and ascorbic acid, as well as reducing the weight loss after storage by about 0.8%. Results in the present study indicated that the LbL edible coating could have the potential to maintain postharvest citrus quality during storage.