Bismuth telluride-Bi2Te3 is the most promising material for harvesting thermal energy near room temperature. There are numerous works on Bi2Te3 reporting significantly different transport properties, with no clear connection to the synthetic routes used and the resultant surface chemistry of the synthesized materials. It is of utmost importance to characterize the constituent particles’ surface and interfaces to get a better understanding of their influence on the transport properties, that will significantly improve the material design starting from the synthesis step. Electrophoretic deposition (EPD) is a promising technique, enabling the formation of thick films using colloidally stabilized suspensions of pre-made nanoparticles, which can enable the study of the effect of surface chemistry, in connection to the synthetic route, on the material's transport properties. In order to explore the differences in surface chemistry and the resultant transport properties in relation to the synthetic scheme used, here we report on Bi2Te3 synthesised through two wet-chemical routes in water (Hydro-) and oil (Thermo-) as the solvents. XRD analysis showed a high phase purity of the synthesized materials. SEM analysis revealed hexagonal platelet morphology of the synthesized materials, which were then used to fabricate EPD films. Characterization of the EPD films reveal significant differences between the Hydro- and Thermo-Bi2Te3 samples, leading to about 8 times better electrical conductivity values in the Thermo-Bi2Te3. XPS analysis revealed a higher metal oxides content in the Hydro-Bi2Te3 sample, contributing to the formation of a resistive layer, thus lowering the electrical conductivity. Arrhenius plots of electrical conductivity vs inverse temperature was used for the estimation of the activation energy for conduction, revealing a higher activation energy need for the Hydro-Bi2Te3 film, in agreement with the resistive barrier oxide content. Both the samples exhibited negative Seebeck coefficient (S) in the order of 160–170 mV/K. The small difference in S of Hydro- and Themo-Bi2Te3 films was explained by the effective medium theory, revealing that the magnitude of S is linearly correlated with the surface oxide content. Based on the findings, TE materials synthesized through thermolysis route is recommended for further studies using soft treatment/processing of pre-made TE materials. EPD platform presented here is shown to clearly expose the differences in the electronic transport in connection to nanoparticle surface chemistry, proving a promising methodology for the evaluation of morphology, size and surface chemistry dependence of electronic transport for a wide range of materials.