Orbital is one of the primary physical parameters that determine materials’ properties. Currently, experimentally revealing the electron occupancies of orbitals under the control of external field remains a big challenge due to the stringent requirements for samples such as the atomically sharp surface or defect-free large-size single crystals. Here, we developed a method with the combination of quantitative convergent-beam electron diffraction and synchrotron powder X-ray diffraction, and demonstrated the visualization of the real-space orbital occupancy by choosing LiCoO2 as a prototype. Through multipole modelling of the accurately measured structure factors, we found the opposite changes of Co t2g and eg orbital occupancies under different electrochemical states which can be well-correlated with the CoO6 octahedra distortion. This robust method provides a feasible route to quantify the real-space orbital occupancy on small-sized particles, and opens up a new avenue for exploring the orbital origin of physical properties for functional materials.