A sensitive and convenient electrochemical method was developed for the determination of rhodamine B by a silica-pillared zirconium phosphate/nafion composite (SPZP/NAF) modified glassy carbon electrode. The SPZP was characterized with scanning electron microscopy and X-ray diffraction. Because of the layer structure and large specific surface area of SPZP, the SPZP/NAF modified glassy carbon electrode showed high electrocatalytic activity toward the oxidation of rhodamine B. Under optimal experimental conditions, the SPZP/NAF modified electrode exhibited a wide linear response to rhodamine B ranging from 0.01 to 5.0 μM and a low detection limit down to 4.3 nM (S/N = 3). This method showed good accuracy, acceptable precision, and reproducibility. This electrode had been applied in the determination of rhodamine B in preserved fruit and chili powder samples. The proposed method provided a useful tool for the assay of rhodamine B in food samples.