The development of the room temperature (RT) gas sensors is absolute need. Hydrothermally and sol-gel derived Co3O4 and Gd0.1Ce0.9O2-δ (GDC) were used to fabricate the novel heterostructures in the ratio of 1:1 Co3O4/GDC, 2:1 Co3O4/GDC and 1:2 Co3O4/GDC. These samples were scientifically analysed through X-ray diffraction (XRD), Field emission scanning electron microscope (FESEM), Energy dispersive X-ray (EDX) spectra, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman, UV–Vis-Diffuse reflectance spectra (DRS) and photoluminescence (PL). XRD, XPS together with FTIR and Raman spectra are the testimonial of the formation of Co3O4, GDC and their heterostructures. Interestingly, the performed gas sensing studies conclusively disclose that these sensors have adequate sensitivity to detect the tested gases at RT. Furthermore, O2− species played crucial role than O2− and O− in chemisorption and gas sensing mechanism. Additionally, 2:1 Co3O4/GDC and 1:2 Co3O4/GDC exhibited an enormous selectivity and highly responsive towards the detection of formaldehyde (CH2O) and ammonia (NH3), respectively. 2:1 Co3O4/GDC/1:2 Co3O4/GDC offered the high response (S) of 106.59/83.52 for CH2O/NH3 gas. In fact, the formation of anisotype p-n/n-p rather than isotype p-p/n-n junctions in 2:1 Co3O4/GDC and 1:2 Co3O4/GDC endowed these two heterostructures to exhibit quick response even at low ppm of selected gases. The outcome of this work might provide strategy for the design of novel sensing materials to detect multiple gases.