Using chitosan (CTS) and sodium carboxymethyl cellulose (CMCNa) as raw biobased materials, polyelectrolyte complex (PEC), which is the product of strong electrostatic interaction between two bio-based polyelectrolytes with opposite charges, was attempted to prepare. To enlarge the reactive contact area between CTS and CMCNa, the crosslinked vacuolar structure of PEC was prepared without addition of cross-linked agent. The preparation conditions had a significant impact on the yield of PEC and the bibulous rate of PEC. When pH, mass ratio of CMC-Na-to-CTS, stirring speed and reaction system temperature were 5, 1:2 [(1 wt% CMCNa, 2 wt% CTS), CMC-Na:CTS = 1:1 (v/v)], 800 rpm, 2 min and 25 °C, the yield of PEC reached 71.2 %. The prepared PEC was characterized by XRD and FT-IR. Afterwards, the antibacterial performance of PEC was examined. The prepared PEC had certain bacteriostatic effect on gram-positive and gram-negative bacteria. The bacteriostasis ratios of PEC against Escherichia coli and Staphylococcus aureus were 18.7 % and 31.3 %, respectively. By controlling the combination parameters of the preparation system, an effective strategy was successfully developed for preparation of biobased PEC with bacteriostatic and crosslinked vacuolar structure through simple physical blending without the application of additional crosslinker.