This work presents the synthesis by plasma of polyhexene (PHe) as an alternative to produce thin films of polyethylene (PE) without catalysts or other chemical compounds. PHe was obtained using 1‐Hexene in glow discharges at 13.5 MHz, 10−1 mBar and power between 40 and 120 W. The results showed that plasma PHe had the typical CC and CH bonds of PE with other bonds, as CC and CO, that indicate unsaturation and oxidation in the polymers. The thermal degradation of PHe starts at 250 °C, 100 °C lower than in PE. However, at T > 500 °C, PHe has more residual mass than PE. In the interval of 20–100 °C, the electrical conductivity of PHe was calculated between 10−11 and 10−8 S/cm. These results suggest that the structures of PHe and PE are similar and that the plasma polymerization of 1‐hexene is an alternative route to obtain oxidized and unsaturated varieties of PE as thin films on different surfaces.