The transfer dynamics and enrichment phenomena of monobutyltin chloride(MBT), dibutyltin chloride(DBT) and tributyltin chloride(TBT) at the water‐surface microlayer (SM) interface were studied. The transport processes of the three compounds at the interface are very fast in the estuarine environment. The mass transfer coefficients are 1.54 m/h for MBT, 2.16 m/h for DBT, 1.56 m/h for TBT. The effect of various factors, including pH, salinity, suspended particulate and temperature, on the adsorptive behavior of TBT in the water's surface microlayer was also studied.