The development of ultrathin dielectrics for low power electronics operations, flexible and printed electronics, and field‐effect‐transistor‐based sensors is still a challenge. Here, monolayers of engineered lipids supported on silicon are reported presenting exceptional mechanical and dielectric properties. The lipid monolayers are stabilized using a simple procedure based on a two‐stage reticulation process in both their aliphatic chains and their head‐group. With a thickness lower than 3 nm, such layers are demonstrated to offer exceptional mechanical and dielectric stability with unprecedented low leakage current and dielectric strength. Surprisingly, the mechanical and dielectric pressures required to rupture/breakdown the monolayers are shown to be similar. These results suggest the presence of a strong correlation between mechanical and dielectric properties, as well as between the mechanisms of rupture and breakdown.