Application of particle image velocity (PIV) techniques for measuringparticle size distribution and total number in an activation chamber of desulfurization system isintroduced. Watersheld algorithm is used to choose the suitable initial gray level threshold whichis used to change the gray level images taken by PIV to black and white ones, then every particle inan image is isolated totally. For every isolating particle, its contour is tracked by the edgeenhancement filter function and kept by Freeman s chain code. Based on a set of particle s chincode, its size and size distribution are calculated and sorted. Finally, the experimental data ofcalcium particles and water drops, separately injected into the activation chamber, and the erroranalysis of data are given out.