Solid Ag/AgCl reference electrodes (RE) with different electrolytes were assembled and characterized in concrete. The performances have been studied with respect to known RE. And the corrosion states of steel have been investigated with respect to embedded and external REs by different electrochemical techniques. Results revealed that half-cell potential of 0.1, 1 and 4.18 M AgCl RE was 20 mV, −30.5 mV and −54.6 mV, respectively. In addition, 4.18 M AgCl RE exhibited the minimum potential drift, the smallest temperature coefficient value and the best reversibility. These corrosion parameters such as rebar potential, corrosion current density (I corr ) and charge transfer resistance (R ct ) obtained for steel with respect to these embedded AgCl REs could clearly differentiate the active condition of steel from the passive condition. Besides, I corr and R ct obtained for steel with respect to external SCE were usually 2 or 3 times larger than these embedded AgCl REs. In such cases embedded AgCl REs could accurately investigate the corrosion rate of steel in concrete. Moreover, the 4.18 M AgCl RE was recommended to monitor the corrosion condition of steel in concrete structure.