Recently, polyacetylene (PA) is receiving a renewed scientific attention due to its electrical properties potentially useful for energy applications (e.g., fabrication of electrodes for batteries and supercapacitors) and unique functional characteristics (e.g., flame retardant, oxygen scavenger, EMI-shielding, etc.). This chemical compound can be obtained in form of a polyacetylene-PVOH copolymers simply by chemical dehydration of poly(vinyl alcohol) (PVOH), which is a very common type of polymer, widely used in packaging and other technological areas. This very inexpensive chemical reaction for the large-scale synthesis of PA/polyvinylenes has been investigated by reacting PVOH with fuming sulfuric acid at room temperature. In this process, PVOH, shaped in form of film, is dipped in fuming sulfuric acid (i.e., H2SO4 at 95-97%) and, after complete chemical-dehydration, it has been mechanically removed from the liquid phase by using a nylon sieve. The reduction process leads to a substantial PVOH film conversion to PA as it has been proved by infrared spectroscopy (ATR-mode). Indeed, the ATR spectrum of the reaction product included all characteristic absorption bands of PA. The reaction product has been also characterized by UV-Vis spectroscopy in order to evidence the presence in the structure of conjugated carbon-carbon double bonds of various lengths. Differential scanning calorimetry (DSC) and thermogravimetric analysis have been used respectively to investigate the PA solid-state cis-trans isomerization and thermal stability in air and nitrogen, respectively.