Butene is a typical component of exhaust gas in the petrochemical industry, the emission of which into the atmosphere would lead to air pollution. In this study, a tubular multilayer dielectric barrier discharge (TM-DBD) reactor was developed to decompose 1-butene at ambient pressure. The experimental results show that a decomposition efficiency of more than 99% and COx selectivity of at least 43% could be obtained at a specific energy density of 100 J/L with an inlet concentration of 1-butene ranging from 100 to 400 ppm. Increasing the volume ratio of O2/N2 from 0 to 20% and the specific energy density from 33 to 132 J/L were beneficial for 1-butene destruction and mineralization. Based on organic byproduct analysis, it was inferred that the nitrogenous organic compounds were the main products in N2 atmosphere, while alcohol, aldehyde, ketone, acid and oxirane were detected in the presence of O2. In addition, the contents of formaldehyde, acetaldehyde, ethyl alcohol, acetic acid and propionic acid increased with an increase in specific energy density, but the contents of propionaldehyde, ethyl oxirane, butyraldehyde and formic acid decreased. Three main pathways of 1-butene destruction were proposed involving Criegee intermediates and ozonolysis of the olefins, and the following degradation could be the dominant pathways rather than epoxidation. Overall, the developed TM-DBD system paved the way for scaling up the applications of plasma technology for gaseous pollutant decomposition.