The plasma-activated water (PAW) containing numerous reactive species can facilitate chitin degradation. Given the intricate interplay between PAW treatment and the diverse activities of chitinolytic enzymes, further investigation is imperative for enhancing the chitin bioconversion efficiency. This study revealed that PAW-treated chitin exhibited improved degradability toward BtLPMO10A, endochitinases OfChtI, OfChtII-B4C1, and exochitinase OfChi-h. Furthermore, H2O2 in PAW boosted BtLPMO10A, whereas the soluble constituents in PAW generated during chitin pretreatment inhibited OfChi-h. Notably, this inhibition effect toward OfChi-h can be mitigated by the addition of β-N-acetylhexosaminidase. In the end, the synergy among the chitinolytic enzyme was also promoted by PAW pretreatment. On this as a basis, a chitin degradation strategy using a combination of PAW treatment and an enzyme cocktail was applied to degrade chitin, achieving a chitin conversion yield of 97% within 2 h. This strategy could also be applied to the degradation of other polysaccharides, such as cellulose.