We propose an experimental protocol for using cold atoms to create and probe quantum dimer models, thereby exploring the Pauling-Anderson vision of a macroscopic collection of resonating bonds. This process can allow the study of exotic crystalline phases, fractionalization, topological spin liquids, and the relationship between resonating dimers and superconductivity subjects which have been challenging to address in solid-state experiments. Our key technical development is considering the action of an off-resonant photoassociation laser on large spin atoms localized at the sites of a deep optical lattice. The resulting superexchange interaction favors nearest-neighbor singlets. We derive an effective Hamiltonian in terms of these dimer degrees of freedom, finding that it is similar to well-known quantum dimer models, which boast a rich variety of valence bond crystal and spin liquid phases. We numerically study the ground state, explain how to tune the parameters, and develop a protocol to directly measure the dimers and their resonating patterns. © 2019 American Physical Society.