Polymers possess a very large inherent capacity for property modifications. The bridge between structure or morphology and mechanical properties is created by the micromechanical processes of deformation and fracture, the “micromechanics.” Developments mainly in electron microscopy (EM) (scanning, transmission, and high-voltage electron microscopy) and scanning force microscopy (SFM) opened up a wide range of experiments previously impossible, including the in situ study of micromechanical processes. These new techniques are reviewed and used to study micromechanical properties of amorphous and semi-crystalline polymers and several toughened polymers. On the basis of the detailed knowledge of micromechanical mechanisms, a new method of polymer modification becomes a realistic possibility, a method of micromechanical construction of new polymeric systems.