Here, it is demonstrated that the stack-and-draw approach can be expanded to unusual materials association and profile geometries to generate fiber assemblies with unprecedented functionalities. This approach relies on the stacking of flat oxide glass slides into a preform, which is then thermally elongated into tens-of-meters-long ribbon fibers with preserved cross-section ratio. Fabrication methodology is introduced. In order to illustrate the versatility of the method, a panel of fibers with diverse geometries and functions is exposed, including glass-only exposed-core fibers for chemical sensing and, upon the insertion of metal electrodes, H-shaped multi-cavity structures and compact, glass-metal fiber optical detectors applied to a gas analysis by means of fiber-tip plasma spectroscopy. It is believed this new approach will offer an attractive, straightforward solution for designing innovative, complex multimaterial fiber platforms with enhanced functionalities.