Relationships between phase morphology and mechanical deformation processes in various electrospun polymer nanocomposite nanofibres (PNCNFs) containing different types of one-, two- and three-dimensional nanofiller have been investigated by transmission electron microscopy using in situ tensile techniques. From the study of the phase structure of electrospun PNCNFs, two morphological standard types are classified for the analysis of deformation mechanisms: the binary system (polymer matrix and nanofillers), and the ternary system (polymer matrix, nanofillers and nanopores on the fibres surface). According to these categories, deformation processes have been characterized, and different schematic models for these processes are proposed. The finding of importance in the present work is a brittle-to-ductile transition in polymer nanocomposite fibres during in situ tensile deformation processes. This unique feature in the deformation behaviour of electrospun PNCNFs provides an optimal balance of stiffness, strength and toughness for use as reinforcing elements in a polymer based composite of a new kind.