The novel TiO and Ni-MOF materials were synthesized and utilized for the detection of permethrin (PET). A highly sensitive solid-state electrochemiluminescence (ECL) sensor was developed based on Ni-MOF@Ru(bpy) and Au NPs@TiO. In this sensing platform, Ru(bpy)-Tripropyl Amine (TPrA) was used as a luminescent signal, Ni-MOF acted as a carrier to carry more luminescent reagents Ru(bpy). Au NPs acted as promoters facilitated electron transport and TiO could further enhance the luminescence intensity of the system by synergistical interaction with Au NPs. The possible mechanisms of signal amplification were investigated. The ECL intensity decreased significantly with increasing PET concentration, enabling the determination of PET amount through the observation of the change in ECL signal intensity (ΔI). Under optimal experimental conditions, the linear range of PET concentration from 1.0 × 10 mol L to 1.0 × 10 mol L, with a detection limit of 3.3 × 10 mol L (3S/N). This method was successfully applied to determine PET in various vegetable samples.