Polylactide (PLA) is an outstanding sacrificial template material for the manufacture of microchannels in a thermosetting matrix. However, the initial thermal degradation temperature of pure PLA is relatively high (about 280°C), which limits its use as a sacrificial template. In this report, we found that TBD, an organic base catalyst, can significantly reduce the thermal degradation temperature of PLA. TBD has higher catalytic activity for the thermal degradation of PLA compared with Tin(II) oxalate (Sn(Oxa)), one catalyst reported in the literature. Moreover, the gaseous products catalyzed by TBD for PLA thermal degradation are mainly lactide, and the formation temperature of the monomer is lower and the yield is higher, which may have potential value for PLA recycling. A combined catalyst, S8T2, was composed of 80% low activity catalyst Sn(Oxa) and 20% high activity catalyst TBD, which can catalyze the rapid degradation of PLA without greatly damaging the mechanical properties of PLA. PLA-S8T2 sacrificial fibers can form high-precision one-dimensional microchannels in the epoxy resin matrix, and 3D-printed PLA-S8T2 sacrificial templates can be used to form three-dimensional microchannels in a thermosetting matrix by vaporization of sacrificial components process (VaSC). These features highlight the great potential of PLA-S8T2 as sacrificial template material for the preparation of the complicated microchannels in the thermosetting matrix. Appendix S1: Supporting Information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.