The combustion properties, flame retardant property, thermal degradation and component of pyrolysis products of calcium alginate fibers were investigated in this paper. The limiting oxygen index value of calcium alginate fibers was 34.4 showing no combustion in the air. The fiber extinguishes instantly when it is moved away from the fire. During the combustion process, the heat release rates (HRR), effective heat combustion (EHC) and total heat release (THR) of calcium alginate fibers were lower than those of cotton fibers, but higher than those of sodium alginate. The carbon dioxide yield rate of calcium alginate fibers was higher than that of cotton fibers but lower than that of sodium alginate. Calcium carbonate and calcium hydroxide, which are beneficial to hamper fibers combustion and diffusion of heat and oxygen, were formed during thermal degradation of calcium alginate fibers. There were 15 kinds of pyrolysis products in gas phase of calcium alginate fibers at 350°C and 45 kinds at 700 °C, while there were 26 kinds of pyrolysis products of sodium alginate at 350°C and 26 kinds at 700°C. Based on a series of study, the flame retardant mechanism of calcium alginate fibers was analyzed.