Poly(3,4-ethylenedioxythiophene) (PEDOT) is an organic conducting polymer that has been the focus of significant research over the last decade, in both energy and biological applications. Most commonly, PEDOT is doped by the artificial polymer polystyrene sulfonate due to the excellent electrical characteristics yielded by this pairing. The biopolymer dextran sulphate (DS) has been recently reported as a promising alternative to PEDOT:PSS for biological application, having electrical properties rivaling PEDOT:PSS, complimented by the potential bioactivity of the polysaccharide. In this work we compared chemical and electrochemical polymerisations of PEDOT:DS in terms of their impact on the electrical, morphological and biological properties of the resultant PEDOT:DS films. Post-growth cyclic voltammograms and UV-Vis analyses revealed comparable redox behaviour and absorbance profiles for the two synthesis approaches. Despite good intrinsic conductivity of particles, the addition of chemically produced PEDOT:DS did not markedly enhance the bulk conductivity of aqueous solutions due to the lack of interconnectivity between adjacent PEDOT:DS particles at achievable concentrations. Scanning electron microscopy revealed significantly greater roughness in films cast from chemically produced PEDOT:DS compared to electropolymerised samples, attributable to the formation of solution phase nanoparticles prior to casting. In cell studies with the L929 cell line, electrochemical polymerisation of PEDOT:DS afforded better integrity of resultant films for surface seeding, whilst chemically polymerised PEDOT:DS appeared to localised at the proliferating cells, suggesting possible applications in drug delivery.