Commercial lithium/thionyl chloride (Li/SOCl2) batteries cannot meet the 3.15 V platform required for most instruments. A hovenia acerba-like assembly constructed with cobalt tetrapyridinoporphyrazine of thickness of 5–15 nm is anchored on acid-functionalized multi-walled carbon nanotubes (CoTAP/MWCNTs), which were prepared using an in situ solid synthesis process. The discharge time of Li/SOCl2 batteries with a voltage greater than 3.15 V catalyzed by CoTAP/MWCNTs is found to be 11 min longer than batteries without catalysts and 4 min longer than those catalyzed by CoTAP alone. The energy of Li/SOCl2 batteries with a voltage greater than 3.15 V catalyzed by CoTAP/MWCNTs is discovered to be 11.44-times higher than batteries with AF-MWCNTs and 6.17-times higher than those catalyzed by bulk CoTAP. This is due to the fact that more CoTAP ultrafine nanoparticulates are anchored on the AF-MWCNTs. These nanoparticulates provide more active sites for the catalytic reaction of SOCl2. The assemblies are shown to have an adsorption-coordination effect on Li ions and to delay the deposition of lithium chloride passive films enhancing battery voltage platforms.