The effect of calcium chloride on dyeing property of polyamide 66 based on reactive anthraquinone dyes with different structures were investigated. The relationship of the structure and properties of the reactive anthraquinone dyes was discussed. Calcium chloride could obviously improve the exhaustion and fixation of the reactive dyes on polyamide 66. The dyes with more sulfonate groups exhibited obviously sensitive to calcium chloride. Compared with the traditional dyeing method, three reactive anthraquinone dyes achieved better building up property and color yields by using calcium chloride at pH value of 7.0. Calcium chloride had obvious dyeing acceleration for polyamide 66. The anthraquinone dye with bifunctional groups could achieve higher exhaustion and excellent fastness on polyamide 66. The mechanism of calcium chloride to exert an influence on dyeing property of polyamide 66 was analyzed. This work is of great significance for improving dyeing performance of reactive dyes on polyamide fiber.