The parent compound $BaBiO_{3}$ of bismuthate high-temperature superconductors (HTSCs) BaBi⁡(Pb)⁢O3 and $Ba⁡(K)⁢BiO_{3}$ with perovskitelike structure exhibits unusual electronic and structural properties, which can be satisfactorily explained if we assume that all charge carriers are in the paired state. However, the prior experiments and the first-principle calculations only indirectly indicate the existence of paired charge carriers in $BaBiO_{3}$. In this work, we report the direct evidence of initially paired electrons and holes in the upper antibonding Bi $6⁢𝑠−O2⁢𝑝_{𝜎*}$ orbital of the neighboring octahedral complexes in the ground state of $BaBiO_{3}$ using the time-resolved x-ray absorption spectroscopy (XAS) to monitor the electron dynamics after the femtosecond resonant 633 nm laser excitation. We observe strong changes in the oxygen 𝐾-edge XAS preedge region, defined by the $Bi6⁢𝑠−O2⁢_{𝑝𝜎*}$ orbitals. We interpret them as a fast (≤0.3 ps) breaking of charge carrier pairs and slower (0.3–0.8 ps) lattice rearrangement from the distorted monoclinic structure into the new metastable state with a cubic lattice, which persists at least up to 60 ps after the excitation. Analysis of the intermediate state at the fast excitation shows that the bond disproportionation and monoclinic distortion of $BaBiO_{3}$ structure are energetically favorable due to the charge carrier pairing. Thus the compound $BaBiO_{3}$ forms a new quantum state that we define as a local pair density wave. Taking into account a large number of similarities between bismuthate and cuprate high-temperature superconductors, we believe that our work will give a new impetus to understanding the nature of superconductivity in perovskite HTSCs.