In this work, we investigate a two-dimensional system of ultracold bosonic atoms inside an optical cavity, and show how photon-mediated interactions give rise to a plaquette-ordered bond pattern in the atomic ground state. The latter corresponds to a 2D Peierls transition, generalizing the spontaneous bond dimerization driven by phonon-electron interactions in the 1D Su-Schrieffer-Heeger (SSH) model. Here the bosonic nature of the atoms plays a crucial role to generate the phase, as similar generalizations with fermionic matter do not lead to a plaquette structure. Similar to the SSH model, we show how this pattern opens a nontrivial topological gap in 2D, resulting in a higher-order topological phase hosting corner states, that we characterize by means of a many-body topological invariant and through its entanglement structure. Finally, we demonstrate how this higher-order topological Peierls insulator can be readily prepared in atomic experiments through adiabatic protocols. Our work thus shows how atomic quantum simulators can be harnessed to investigate novel strongly correlated topological phenomena beyond those observed in natural materials.