Owing to its inherent non‐trivial geometry, the unique structural motif of the recently discovered kagome topological superconductor AV3Sb5 (A = K, Rb, Cs) is an ideal host of diverse topologically non‐trivial phenomena, including giant anomalous Hall conductivity, topological charge order, charge density wave (CDW), and unconventional superconductivity. Despite possessing a normal‐state CDW order in the form of topological chiral charge order and diverse superconducting gaps structures, it remains unclear how fundamental atomic‐level properties and many‐body effects including Fermi surface nesting, electron–phonon coupling, and orbital hybridization contribute to these symmetry‐breaking phenomena. Here, the direct participation of the V3d–Sb5p orbital hybridization in mediating the CDW phase transition in CsV3Sb5 is reported. The combination of temperature‐dependent X‐ray absorption and first‐principles studies clearly indicates the inverse Star‐of‐David structure as the preferred reconstruction in the low‐temperature CDW phase. The results highlight the critical role that Sb orbitals play and establish orbital hybridization as the direct mediator of the CDW states and structural transition dynamics in kagome unconventional superconductors. This is a significant step toward the fundamental understanding and control of the emerging correlated phases from the kagome lattice through the orbital interactions and provides promising approaches to novel regimes in unconventional orders and topology.