W1-1.0C steel was chromized at 1173 K with double glow plasma surface alloying process, and the distribution of Fe, Cr, and C contents in the chromized layer was measured using glow discharge spectrum analysis (GDA). The behavior and mechanism of carbon migration during the formation of chromized layer were studied through thermodynamic analysis and calculation. The gradient of carbon chemical potential was regarded as the driving force of carbon migration. An equation was derived to describe the carbon content varying with the chromium content within the carbon-rich region. The calculated results from the equation approximated closely to the experimental ones.