Conventional multi-material multi-layer flexible packaging offers excellent properties. However, it has recycling challenges, necessitating a shift to mono-material multi-layer flexible packaging for example all-polyethylene (PE) packaging which can be tailored through various synthesis and processing methods for different layers. In this work, we study how the key molecular properties (number-average molecular weight ( Mn), weight-average molecular weight ( M w), molecular weight distribution (MWD), comonomer content (short chain branching)) and machine direction orientation (MDO) process draw ratio (MDX) influence the final morphology and mechanical properties of MDO-PE films which are intended as the outer layer of mono-material all-polyethylene multi-layer flexible packaging. Five PE grades and various blends were extruded and blown into films. Selected blown films were machine direction oriented to obtain the final MDO-PE films. Furthermore, one selected PE blown film was processed at different MDO process draw ratios while keeping other process parameters constant. From the molecular properties point of view, the higher molecular weight fractions provide a higher possibility for uniform stretching whereas lower molecular weight fractions provide a higher natural draw ratio and therefore higher modulus and stiffness enhancement. Further, the results show that increasing MDO process draw ratio leads to more fibrillation and increased crystallinity. Consequently, the tensile modulus and stiffness at the higher draw ratios increase as well and are comparable to conventionally used polymers in outer layers of multilayer flexible packaging. Thus, this work demonstrates that MDO-PE films with enhanced modulus can provide sufficient stiffness for the design of outer layer of mono-material multi-layer all-PE packaging which presents higher potential for mechanical recyclability.