In this study, meta-aramid fibres were pretreated with 2-phenoxyethanol under different conditions to investigate the effect of 2-phenoxyethanol on the dyeing of aramid at low temperature (95 °C). Structural alteration of the pretreated fibres was reflected by thermogravimetry and Fourier transform infrared spectroscopy, indicating more H-bonds, lower crystallinity, and slightly lower thermal stability. The change in structure showed that 2-phenoxyethanol combined with the fibre macromolecules and resulted in swelling of the fibre. Creation of a biphasic system through the addition of 2-phenoxyethanol to the dyeing solution resulted in the cationic dye being partitioned more towards the 2-phenoxyethanol-rich phase than the aqueous phase. The cross-sections of the dyed fibre suggested that the meta-aramid fibre could be dyed more thoroughly with an appropriate concentration of 2-phenoxyethanol. The colour value of aramid fabric was tested by varying the concentration of 2-phenoxyethanol and the temperature of pretreatment, indicating a dramatic improvement in dyeing performance to aramid after 2-phenoxyethanol pretreatment. 2-Phenoxyethanol pretreatment and low-temperature dyeing can overcome the problems of chemical and energy waste while producing a satisfying colour.