The effects of pretreatment conditions, including the addition of a phase-transfer catalyst, on the benzylation of ramie fiber were investigated in this study. Raw and benzylated ramie fibers were dyed in supercritical carbon dioxide, and the color strength (K/S) of the ramie fiber was measured by ultraviolet–visible spectroscopy. An obviously improved dyeing capability of the benzylated ramie fiber, that is, a better level-dyeing property and a higher K/S, was achieved. Moreover, the color strength of the ramie fiber, indexed as the value of K/S, increased significantly with the degree of substitution of the benzylated ramie fiber. The raw and modified ramie fibers were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry.