The removal of sulfur from SO2 containing flue gas is improved by adsorbing SO2 into solution with manganese ions as catalyser, however, burnt lime slurry has to be added to modify solution pH and the CaSO3 by-product is of low economic value. In this paper a novel one step process for simultaneous manganese leaching-desulfurisation of flue gas is presented. An investigation of the effect of process parameters included flow rate and SO2 concentration in flue gas, adsorbing time, solution to solid mass ratio, leaching time, and their impact on the oxidation and removal of SO2 from flue gas. The catalysing mechanism of manganese ions on the oxidation and SO2 removal was demonstrated by calculation of the species originating from manganese ions and SO2 in the solution according to solution chemistry. SO2 removal in the adsorbing solution took place at pH 5 - 6, where manganese ions dominantly occurred as Mn2+, and the chain reactions for oxidation of SO2 starting from HSO3- were improved by the presence of Mn2+. SO2 bearing flue gas was effectively desulfurised by leaching rhodochrosite (MnCO3), with desulfurisation of the flue gas and modifying the solution pH being achieved simultaneously, and MnSO4 of high economic value recovered from the leachate. 85 per cent manganese leaching and over 70 per cent desulfurisation of the SO2-bearing flue gas were achieved with only one adsorption stage under optimum conditions.