The purpose of this research is to have a clearer understanding of the resource value of electrolytic Zn anode slime, explore its fine structure and treat it in a classified manner. In this paper, the composition, content and distribution of Pb, Mn and Zn in electrolytic Zn anode slime during one production cycle were studied under typical working conditions of enterprises, by using the method of μ-XRF combined with mm-XRF. Based on heatmap and cluster analysis, the resource value of anode slime at different points in the electrolytic Zn silting area and the conventional area was evaluated. The research results were as follows: (1) There were two different areas of electrolytic Zn anode slime: the silting area and conventional area. Between these, the silting area accounted for approximately 15% of the total number of anode plates, and there were significant differences between these areas in terms of surface element content, surface morphology, slime thickness and water content. (2) In the silting area, 3.9 mm away from the Pb-based anode plate surface, there were lumps with fluorescence counting intensity that was close to that of pure Pb. (3) Anode slime at a thickness of 0.1 mm in the silting area could be classified as a type of resource. The resource attributes were categorized using a complete-linkage algorithm and the actual demand of Zn hydrometallurgy enterprises for recycling anode slime from the leaching process, for those with ≥45% Mn content and <20% Pb content. High-Pb resources include 0−1.5 mm (CAP), 0−1.4 mm (SAP) and 6.3−7.0 mm (SAP). A low-Pb, high-Mn and high-Zn resource was identified at 2.9−6.0 mm (SAP). Low-Pb, high-Mn and low-Zn resources include 1.6−6.0 (CAP), 1.5−2.8 mm (SAP) and 6.1−6.2 mm (SAP).