Nanocomposites can offer a platform to conjugate biorecognition features of aptamer with unique size-dependent properties of a given material, which can autoprobe the binding event based on their electroactive characteristics. Herein, we design electroactive switchable aptamer probes based on co-doped single-phase semiconducting materials employing the cyclic voltammetry method to record the current signal at each step of electrochemical characterization. To do so, we utilized a facile hydrothermal method assisted by co-precipitation method such as Co-Fe-co-doped Ba0.5Sr0.5Zr0.1Y0.1O3-δ (CF-BSZY) and tuned the alignment of the energy band structure of the material to amplify the output of theelectrochemical signal. Atvarious steps, changes occurred in the electrochemical properties at the surface of CF-BSZY. The binding of the ssDNA with prepared materials enhances the current signal by the interaction with the target (ochratoxin A (OTA)) depressing the current signal and facilitating the construction of a novel design of electrochemical aptasensor. As a proof of concept, an electrochemical aptasensor for the detection of ochratoxin A (OTA) in rice samples has been developed. The electrochemical aptasensor provides a limit of detection (LOD) of 0.00012μM (0.12nM), with a linear range from 0.000247 to 0.74μM and sound OTA recovery in real samples. The developed aptasensor is simply designed andis free of oligonucleotide labeling or decorative nanoparticle modifications. The proposed mechanism is generic in principle with the potential to translate any type of aptamer and target binding event into a detectable signal; hence, it can be largely applied to various bioreceptor recognition phenomena for subsequent applications.