Several cyclic ammonium-based ionic liquids (ILs) with allyl substituent are synthesized, these allyl substituent ILs have high ionic conductivity (up to 4.72mScm−1 at 30°C) and wide electrochemical window of 5V. The electrochemical behaviors of two organometallic redox couples Fc/Fc+ (ferrocene/ferrocenium) and Cc/Cc+ (cobaltocene/cobaltocenium) have been studied in these ILs, the calculated Stokes–Einstein product (Dη T −1) of ferrocene in ILs is larger than that of cobaltocenium in ILs. The self-diffusion coefficients of cation and anion in these ILs are studied using pulsed gradient spin-echo NMR technique. There are very few reports where electrochemically derived diffusion coefficients and self diffusion coefficients are available for comparison, so a new key concept in electrochemistry could be developed in this paper.