The development of gas sensor with innovative designs is highly desirable for widespread deployments of sensors in applications of monitoring indoor air quality and industrial safety. Herein, an approach is put forward to substantially improve gas sensing performance via electrospinning of metal ion and cross-linked polymer to porous and hetero indium trioxide (In2O3) ribbon combined with cobaltosic oxide (Co3O4) particles. The structural evaluation was systematically discussed and the content of the Co3O4 was subtly regulated. The gas sensing results indicated that the obtained vacancy oxygen and adsorbed oxygen-abundant In2O3-Co3O4ribbons exhibited significantly high response towards volatile organic compounds (VOCs) encompassing acetone (52, 280 °C) and formaldehyde (39, 260 °C), which can be ascribed to hierarchical porous hetero-structures, ion mismatch and catalytic property of p-type Co3O4. This facile way sheds light on the rational design of gas sensitive materials via structure and composition engineering, resulting in facilitating the gas molecules adsorption and diffusion.