Surface water can be divided into three layers from top downward: surface microlayer (SML, thickness≤50 μm), subsurface layer (SSL, ≈25 cm) and surface layer (SL, 1–5m), among which the SML plays an important role on sea-air interaction because of its unique physical-chemical property. Carbon dioxide system including DIC (dissolved inorganic carbon), Alk (alkalinity), pH and pCO2 (partial pressure of CO2) in multilayered waters of the Yellow Sea was studied for the first time in March and May 2005. The results show that: DIC and Alk are obviously enriched in SML. The contents of DIC, Alk and pCO2 become lower in turn from SML, SSL to SL, higher in March and lower in May, whereas for pH it was opposite. The relationship between DIC and Alk is clearly positive, but negative between pH and pCO2. Meanwhile, pCO2 and temperature/salinity is also in positive relation, pCO2 decreases with latitude increase. DIC and Alk show a similar variation trend with the maximum at 02:00–03:00, but pH and pCO2 show an opposite pattern. In addition, the distribution patterns are similar to each other in the three layers. The Yellow Sea is shown to be a sink of atmospheric CO2 in spring by two methods: (1) comparing pCO2 in seawater and atmosphere; (2) turning direction of “pH-depth” curve. Calculation on the base of pCO2 data in SML in four models shows that carbon flux in spring in the area was about -6.96×106 t C. Surface water can be divided into three layers from top downward: surface microlayer (SML, thickness≤50 μm), subsurface layer (SSL, ≈25 cm) and surface layer (SL, 1-5m), among which the SML plays an important role on sea-air interaction because of its unique physical-chemical property. Carbon dioxide system including DIC (dissolved inorganic carbon), Alk (alkalinity), pH and pCO2 (partial pressure of CO2) in multilayered waters of the Yellow Sea was studied for the first time in March and May 2005. The results show that: DIC and Alk are clearly enriched in SML. The contents of DIC, Alk and pCO2 become lower in turn from SML, SSL to SL, higher in March and lower in May, while for pH it was opposite. The relationship between DIC and Alk is clearly positive, but negative between pH and pCO2. pCO2 and temperature / salinity is also in in relation, pCO2 decreases with latitude increase. trend with the maximum at 02: 00-03: 00, b The addition of the distribution patterns are similar to each other in the three layers. The Yellow Sea is shown to be a sink of atmospheric CO2 in spring by two methods: (1) comparing pCO2 in seawater Calculation of the base of pCO2 data in SML in four models shows that carbon flux in spring in the area was about -6.96 × 10 6 t.