We present here a systematic investigation to understand why aqueous sodium alginate can only be electrospun into fibers through a blend with another polymer; specifically, polyethylene oxide (PEO). We seek to examine and understand the role of PEO as the "carrier polymer". The addition of PEO favorably reduces electrical conductivity and surface tension of the alginate solution, aiding in fiber formation. While PEO has the ability to coordinate through its ether group (-COC-) with metal cation like the sodium cation of sodium alginate, we demonstrate in this study using PEO as well as polyvinyl alcohol (PVA) that coordination may have little effect on electrospinnability. More importantly, we show that PEO as carrier polymer provides molecular entanglement that is required for electrospinning. Since the selected carrier polymer provides the necessary entanglement, this carrier polymer must be electrospinnable, entangled and of a high molecular weight (more than 600 kDa for PEO). On the basis of these requirements, we stipulate that the PEO-PEO interaction of the high molecular-weight entangled PEO is key to "carrying" the alginate from solution to fibers during electrospinning. Further, using the resulting understanding of the role of PEO, we were able to increase the alginate concentration by employing a higher molecular-weight PEO: up to 70 wt % alginate using 2000 kDa PEO and, with, the addition of Triton X-100 surfactant, up to 85 wt % alginate, higher than previously reported.