In this work, the oxidative conversion of propane was studied using a dielectric barrier discharge microreactor. This generates a cold microplasma at atmospheric pressure and ambient temperatures. Surprisingly, large amounts of products with molecular weight higher than propane, such as C-4 and C-4+, were mainly observed due to C-C bond formation, in contrast to what is usually observed for this reaction when it is carried out under thermal activation, which leads to cracking products. A chemical kinetic model was developed to better understand the radical reaction network. Interestingly, the results suggest that (i) at lower level of propane conversion the model can nicely predict the experimental results and (ii) depending on the radical density the product selectivity can be tailored. In particular, at higher radical density, enhanced C-C bond formation was observed.