The unsteady dispersion of a solute band by a steady pressure-driven flow in a semicircular microchannel is theoretically studied via the generalized dispersion model. Considering an irreversible first-order reaction at the curved wall while assuming a no-flux boundary condition at the flat wall, analytical solutions are obtained for the exchange, convection, and dispersion coefficients as well as the dimensionless forms of solute concentration and mean solute concentration. The solutions are obtained assuming an initial solute band of arbitrary cross-sectional shape and axial distribution and the results are presented for both circular and semicircular shapes with the uniform distribution being a special case of the latter. Besides the general solutions, special solutions are also derived for uniform velocity and no-reaction cases. In the following, the influences of the initial concentration distribution and the Damköhler number, a measure of the reaction rate, on the transport coefficients and the concentration distribution are deeply investigated. It is demonstrated that the combination of the initial concentration distribution and the Damköhler number specify the variations of the transport coefficients in the short term but the Damköhler number is the only parameter dominating the long-term values: the exchange and convection coefficients are increasing functions of the Damköhler number whereas the opposite is true for the dispersion coefficient. Moreover, we show that, provided the solute injection is appropriately positioned and shaped, liquid-phase transportation with little dispersion is possible in typical microchannels utilizing semicircular geometry.