A facile and high yield centrifugal spinning technique known as Forcespinning® (FS) was used to develop unique microstructures consisting of PLA microbeads along alginate fibers. Morphological variation and structural features appeared in the field-emission scanning electron micrographs for the PLA-alginate composites and dried PLA-alginate films from precursor emulsions at constant PLA and varied alginate contents. Shrunk and deflated microbeads were observed for composites whilst spherical beads were evident for the PLA control. Furthermore, PLA was found surrounding the alginate when the alginate was present at 0.24 wt% or lower, while alginate (mushroom-like structures), were seen protruding through the PLA layer at ≥0.34 wt% alginate. Rheological characterization of the composite emulsions revealed that the filler (alginate) provided shear thinning properties including pseudoplasticity, desirable for printing and other related applications in contrast to the Newtonian flow shown by the PLA control. Along with infra-red spectroscopy, the nanocomposites were further characterized using thermal gravimetry and differential scanning calorimetry featuring reversible events influenced by heat capacity and irreversible kinetic/thermodynamic counterparts. The work provides a comprehensive investigation of biocompatible networks of PLA-alginate microbeads embedded in nano-sized fibers and the prospective application of these microbeads as a drug delivery system.