For the first time, low transition temperature mixtures – LTTM based on sugars: fructose (Fruc), glucose (Gluc) or sucrose (Suc), and glycerol (G) are prepared, characterized by DSC and applied as potato starch plasticizers. Sugar‐based LTTM exhibits good plasticizing activity leading to homogenous transparent, flexible thermoplastic starch (TPS) materials. Mechanical, dynamic mechanical (DMA), X‐ray diffractometry (XRD), and FTIR analysis of obtained TPS/LTTM films are performed for their relative comparison. For TPS/Fruc:G films, tensile strength (TS) and Young's modulus (YM) decreases and elongation at break (EB) increases with increase of G. However, for TPS/Gluc:G molar ratio of Gluc to G did not affect significantly on films mechanical properties. Comparing two monosugars, i.e., Gluc and Fruc, TPS/Gluc:G materials exhibit slightly higher TS (4.8–5.8 MPa) but lower EB (44–61%) in comparison with TPS/Fruc:G films (TS 3.2–5.0 MPa; EB 90–115%) at 25 °C, RH 50%. LTTM as whole mixture of components led to TPS products with not only higher TS, YM but even EB in comparison with films where sugars and G were added separately into starch. Mutual interaction between sugar, polyol and starch is confirmed by DMA. XRD reveals that starch with LTTM undergone amorphization and TPS/Suc:G 1:6 is the most amorphous among investigated TPS films.