Lignocellulosic biomass as a renewable and valuable resource has been a very active research area during recent years. Ionic liquids (ILs) are an attractive approach for the pretreatment of lignocelluloses. In this work, a series of pyrrolidinium-based ionic liquids were prepared simply and were investigated for the pretreatment of corn stalk at 90 °C for 30 min. The characteristics of regenerated lignin and cellulose-rich materials were determined by Fourier transform infrared spectroscopy (FTIR) analysis. Both ILs and ILs/H2O were studied. Notably, 10.17% lignin based on the original corn stalk was recovered with [Hmp]Cl-pretreatment; 21.34% and 15.83% reducing sugar based on the original corn stalk were observed during pretreatment with [Hmp]HSO4/H2O and [Hmp]Cl/H2O pretreatment, respectively; 80.54% of reducing sugar was obtained based on the cellulose-rich materials with [Hmp]Cl/H2O-pretreatment. Also, the glucose and cellobiose yields were 73.82% and 8.64%, respectively.