Experimental investigations of the diode-laser-induced ignition of potassium picrate (KP) with a multi-walled carbon nanotube (MWNT) additive are presented in this article. KP/MWNT composites with varying contents were prepared directly by adding different quantities of MWNTs to a KP solution after the last synthesis step. Due to capillary action, the MWNTs homogeneously coated the surface of the KP, and some KP crystallized inside the MWNTs. The samples were characterized by scanning and transmission electron microscopy, differential thermal analysis, and laser ignition tests. At a constant laser power density, the doped KP showed a much shorter ignition delay time than the undoped KP (from 28.8 ms to 4.5 ms). Therefore, the higher the dopant MWNT ratio is, the shorter the ignition delay time is. Additionally, the more MWNTs are used to dope KP, the lower the required ignition power is.