Conductive materials are valuable supports and widely applied in electrochemical analysis. In the current article, a mesoporous organosilica sphere (S,S)-CPMO-3 with the chiral group and electroactive units is presented. The organosilicon framework is composed of free ions belonging to the ionic liquid and the chiral group arising from (1S,2S)-1,2-diaminocyclohexane. Next, a bare electrode was modified by the as-synthesized composite material to construct the new electrochemical sensor (S,S)-CPMO-3-GCE. It was observed that (S,S)-CPMO-3-GCE exhibited favourable enantioselective recognition in the response of the peak current (Ip) and the peak potential (Ep) to the different configurations of amino acids. Taking tryptophan as an example, the value of IL/ID is 13.84 and the peak-to-peak potential approaches 48 mV. In addition, cysteine and tyrosine were successfully distinguished by the sensor. In summary, this study not only introduces a route for the synthesis of a conductive material, but also opens up its further potential in enantioselective recognition.