It has recently been shown that liquid ammonia treatment (water-based process) is very effective in improving the wrinkle recovery, dimensional stability, and resistance to abrasion of the all-linen fabrics. In this study the changes in the fine structure were characterized by measuring the crystallinity and sorption properties of the linen fabrics. In addition, the effect of liquid ammonia on the surface properties of the linen fibers was investigated. X-ray analysis showed that liquid ammonia treatment did not significantly affect the ratio of crystalline and amorphous regions, but a partial recrystallization occurred in the crystalline part, resulting in mixed cellulose I and III lattices in the linen substrates. Although the moisture regain and iodine sorption capacity of the treated linen substrates increased, water retention values, however, were decreased significantly by the intracrystalline swelling treatment.