The authors show that micron size fibers comprised of semiconductor and metallic materials can be purified or doped, recrystallized or have the constituents rearranged into a variety of structures with device prospects. The molten core drawing method allows scalable fabrication of novel core fibres with kilometre lengths. With metal and semiconducting components combined in a glass-clad fibre, CO2 laser irradiation was used to write localised structures in the core materials. Thermal gradients in axial and transverse directions allowed the controlled introduction, segregation and chemical reaction of metal components within an initially pure silicon core, and restructuring of heterogeneous material. Gold and tin longitudinal electrode fabrication, segregation of GaSb and Si into parallel layers, and Al doping of a GaSb core were demonstrated. Gold was introduced into Si fibres to purify the core or weld an exposed fibre core to a Si wafer. Ga and Sb introduced from opposite ends of a silicon fibre reacted to form III-V GaSb within the Group IV Si host, as confirmed by structural and chemical analysis and room temperature photoluminescence.