Mass transfer rates in vertical gas‐liquid flow were measured by an electrochemical technique. The flow regimes studied were slug, churn and annular. Average mass transfer coefficients in gas‐liquid flow could be correlated by expressions similar to those for single phase flow. Fluctuations in local mass transfer coefficient could be used to indicate flow regimes. Average wall shear stress determined from the average mass transfer coefficients agreed with values calculated from measurements of pressure drop, void fraction and flow rate, provided flow reversals did not occur. The results indicate that the electrochemical technique could be used to measure wall shear stress in accelerating gas‐liquid flows, such as critical flow.