All-polymer multilayer hollow core photonic fiber preforms were fabricated using consecutive deposition from a solvent phase of two polymers with high and low refractive indices (RI). Processing techniques for two polymer pairs—polystyrene (PS)/poly(methyl methylacrylate) (PMMA) and polycarbonate (PC)/poly(vinylene difloride) (PVDF)—were established. The fabrication process involved consecutive film deposition by solvent evaporation of polymer solutions on the inside of a rotating PMMA or PC tube, used as a cladding material. By injecting right volumes of the polymer solutions into a spinning tube the thickness of each layer could be reliably controlled from 20 to 100 μm. Proper selection of solvents and processing conditions was crucial for ensuring high optical and mechanical quality of a resultant preform, as well as compatibility of different polymer films during co-deposition. Preforms of 10 layers for PMMA/PS material combination and 15 layers for PVDF/PC were demonstrated. Fabrication of preforms with higher number of layers is readily possible and is only a question of preform fabrication time. An alternative method of preform fabrication by co-rolling of polymer bilayers is also presented in this paper, drawing of PMMA/PS, PVDF/PC fibers with up to 32 layers is demonstrated.