Traditional composting is a well-suited biotechnology for on-farm management of livestock manure (LM) but still leads to the release of toxic micropollutants and imbalance of nutrients. One in situ exoenzyme-assisted composting has shown promise to ameliorate the agronomical quality of end products by improving humification and polymerization. The naturally occurring extracellular laccase from microorganisms belongs to a multicopper phenoloxidase, which is verified for its versatility to tackle micropollutants and conserve organics through the reactive radical-enabled decomposition and polymerization channels. Laccase possesses an indispensable relationship with humus formation during LM composting, but its potential applications for the harmless disposal and resource utilization of LM have until now been overlooked. Herein, we review the extracellular laccase-aided humification mechanism and its optimizing strategy to maintain enzyme activity and in situ production, highlighting the critical roles of laccase in treating micropollutants and preserving organics during LM composting. Particularly, the functional effects of the formed humification products by laccase-amended composting on plant growth are also discussed. Finally, the future perspectives and outstanding questions are summarized. This critical review provides fundamental insights into laccase-boosted humification that ameliorates the quality of end products in LM composting, which is beneficial to guide and advance the practical applications of exoenzyme in humification remediation, the carbon cycle, and agriculture protection.