Although sodium alginate (SA) could not be electrospun from its aqueous solution, SA-based electrospun nanofibers can be fabricated with the help of polyethylene oxide (PEO). In this study, the influence of PEO on the electrospinnability of SA aqueous solution was investigated and the roles of chain entanglements and conformations of the blend system were emphasized. It was found that a little amount of PEO100 with high molecular weight could improve the electrospinnability of SA aqueous solution. However, a large amount of PEO2 with low molecular weight had no positive effect on the electrospinnability of SA aqueous solution. Dynamic laser light scattering (DLLS) results showed that only when the PEO molecular chains in aqueous solution were in an entangled state, PEO can enhance the electrospinnability of SA aqueous solution. The further study on theological measurements showed that SA molecular chains could not form significant entanglements for the electrospinning even when the SA solution concentration approached concentrated regime. SA molecular chains are closely "overlapped" due to its rigid and extended conformation and cannot form effective chain entanglement. The main contribution of PEO100 to improve SA electrospinnability is offering entanglement sites and thereby enhancing the applicable entanglement degree of the blend system. Whereas, although the chain interaction between PEO2 and SA may improve slightly the flexibility of SA chains, the significant chain entanglements of the blend solution is not achieved. Three molecular models are proposed to depict visually the effect of PEO with different molecular weights on chain conformations and entanglements of SA. (C) 2009 Elsevier Ltd. All rights reserved.