Lignin peroxidase (LiP), which has been studied extensively in white-rot basidiomycetes and their potential to degrade dyes from textile wastewater, plays a role in the biodegradation of lignin from pulp and paper industry wastewater, as well as agricultural waste. Lignin peroxidase (LsLiP) was successfully purified from the newly isolated Lentinus squarrosulus MPN12 with a 47.1-fold purification and a 15.7% yield. After 48 h-incubation, LsLiP was able to decolorize all tested dyes up to 92% for Acid Blue 62 (NY3), followed by Porocion Brilliant blue HGR (PB, 73.5%), Acid Blue 281 (NY5, 70.5%), Acid Blue 113 (IN13, 61%), Acid red 266 (NY7, 56%), and 34.5% for Acid red 299 (NY1), compared to the negative control with the heat-denatured enzyme. The biodegradation potential of LsLiP was further suggested by the change of lignin structure based on Fourier transform infrared (FTIR) analyses. Lignin structure was noticeably changed before and after LsLiP treatment, especially in the fingerprint regions (1600 to 1000 cm-1) and 2930 cm-1 corresponding to the stretching vibrations of various groups in lignin. Thus, LsLiP has potential application in both enzyme-based decolorization of synthetic dyes and lignin biodegradation.