Combing the metal organic frameworks (MOFs) with surface enhanced Raman scattering (SERS) hybrid substrates have been to a focus of high-efficiency SERS detection. In this study, we developed a MOF-SERS substrate by immobilizing the thioctic acid-modified gold nanoparticles (AuNPs) onto the surface of UiO-66 through electrostatic interactions. The effect factor (EF) of UiO-66/AuNPs substrates for the cationic malachite green, methylene blue and saffron T were 2.12×104, 4.46×104 and 7.20×104, two orders of magnitude higher than the EF of 1.43×102, 2.54×102 and 1.73×102 for the anionic lemon yellow, sunset yellow and congo red. Overall, UiO-66/AuNPs substrates can selectively improve the detection sensitivity of cationic pigments by electrostatic adsorption and are a highly efficient SERS sensor material with promising applications.