Sub-lithographic dimensioned air gap formation and related structure are disclosed. In one embodiment, a method includes forming a dielectric layer including interconnects on a substrate; depositing a cap layer on the dielectric layer; depositing a photoresist over the cap layer; patterning the photoresist to include a first trench pattern at most partially overlying the interconnects; forming a spacer within the first trench pattern to form a second trench pattern having a sub-lithographic dimension; transferring the second trench pattern into the cap layer and into the dielectric layer between the interconnects; and depositing another dielectric layer to form an air gap by pinching off the trench in the dielectric layer.