•Ex-situ catalytic technology was used to co-pyrolysis C. odorata and soapstock.•The optimal catalytic parameters and C. odorata and soapstock ratio were determined.•Soapstock proved to be a good hydrogen supplier to increase the quality of bio-oil. Fast microwave-assisted catalytic co-pyrolysis of Chromolaena odorata (C. odorata) and soybean soapstock with HZSM-5 as an ex-situ catalyst was investigated. Effects of catalytic temperature, feedstock: catalyst ratio and C. odorata: soybean soapstock ratio on the yield and composition of the bio-oil were discussed. Results showed that catalytic temperature greatly influenced the bio-oil yield. Co-pyrolysis of C. odorata and soybean soapstock improved the bio-oil yield, and the maximum bio-oil yield of 55.14% was obtained at 250 °C. However, the addition of HZSM-5 decreased bio-oil yield but improved the quality of bio-oil. Moreover, the proportion of oxygen-containing compounds decreased dramatically with the addition of soybean soapstock. The C. odorata: soybean soapstock ratio of 1:2 and feedstock: catalyst ratio of 2:1 were the optimal condition to upgrade the bio-oil. In addition, the resulted biochar contained various essential elements and could be used as soil repair agent.