Developing a suitable initiation for the energetic materials that respond to a low-power near-infrared laser can aid in replacing the current expensive and bulky laser-initiation systems. Here, we report on a system of molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystals that manifest ultrabroad absorption (200-2500 nm) characteristics as well as noteworthy very fast self-assembly behaviors. The very narrow highest occupied molecular orbital-lowest unoccupied molecular orbital gap enables N,N,N',N'-tetramethyl-p-phenylenediamine and tetrahalo-1,4-benzoquinones (TMPD-TXBQ) cocrystals to have a great light-harvesting ability in the near-infrared range. When irradiated with a low-power hand-held 808 nm laser with an input energy of only 40 mJ or a power density of 260 mW·cm-2, these TMPD-TXBQ cocrystals immediately undergo an efficient photothermal conversion followed by a dramatic exothermic thermal polymerization reaction due to the face-to-face D-A-D-A stacking in these cocystals to achieve a temperature as high as 318.9 °C. This temperature is high enough for a thermal initiation of most common energetic materials, and thus this TMPD-TXBQ cocrystal can potentially act as a near-infrared laser initiator that is compact, lightweight, and cost-effective.