To relate froth structural information with mineral flotation performance, segmentation analysis was performed on froth images characterized by fully occupied convex bubbles with white spots effect. An improved valley edge detection method was proposed to extract structural features and overcome fake white spot edges seriously affecting the segmentation performance. After preprocessing, detection template was designed based on the local minimal intensity, and a binary image containing segmented boundaries was obtained by applying logical rules, thinning and filtering. Statistical features such as bubble size were estimated for control purpose. Experimental results demonstrate that the proposed method avoids over-segmentation or ill-segmentation caused by uneven illumination, and the industrial application reveals the reliability of bubble size estimation.