Introducing molecular nanolayers (MNLs) is attractive for enhancing the stability of, and inducing unusual properties at, inorganic thin film interfaces. Although organic molecules anchored to inorganic surfaces have been studied extensively, property enhancement mechanisms underpinned by molecular assemblies at inorganic thin film interfaces are yet to be revealed and understood. Here, ab initio molecular dynamics simulations of tensile strain of Au/MNL/Au thin film nanosandwich models provide insights into molecularly induced strain hardening and toughening. Au/MNL/Au nanosandwiches support up to approximate to 30% higher stresses and exhibit up to approximate to 140% higher toughness than pure Au slab models. Both hardening and toughening are governed by molecular length and terminal chemistry in the MNL. Strong Au/MNL interface bonding and greater molecular length promote defect creation in Au, which results in strain hardening. Accommodation of increasing post-hardening strains in the MNL mitigates the stress increase in the Au slabs, delays interface fracture, and contributes to toughening. Remarkably, toughening correlates with equilibrium interface strain, which could be used as a proxy for efficiently identifying promising inorganic/MNL combinations that provide toughening. Our findings are important for the discovery and design of inorganic-organic interfaces, nanomaterials, and composites.