Pilling is a common and unresolved problem in knitted fabrics, especially for the cellulose fiber blended fabrics, which not only causes an unattractive appearance and an uncomfortable handle, but also reduces the added value of the products. In this study, four different kinds of knitted fabrics were treated with 2,4,6-trichloropyrimidine (TLP) alkaline emulsion by dipping and pad–dry–cure modification processes. The surface morphology and chemical structure of original and treated fabrics were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The anti-pilling performance, thermal properties, physical and mechanical properties and color features of treated fabrics were also evaluated. The results indicated that TLP was successfully covalently crosslinked onto the surface of the cellulose fibers. The dipping process resulted in a better anti-pilling property than that of the pad–dry–cure process, and both treatments could bring about an excellent anti-pilling property and outstanding laundering durability. A pilling grade of 4.5 was achieved for the treated polyester/viscose (T/V) fabric with the dipping process even after 20 washing cycles. In addition, the treated fabrics displayed an enhanced antistatic property and still maintained a soft handle. Besides, the bursting strength and air permeability of treated samples were found to have a slight deterioration, while no apparent differences were found in the color parameters and colorfastness of dyed fabrics. The above results demonstrate that 2,4,6-trichloropyrimidine has the potential application prospect in the functional finishing and home-caring of textiles.