ZnSn(OH)(6) and binary-component SnO(2)-ZnSn(OH)(6) were introduced as affinity probes for phosphopeptide enrichment for the first time. Two strategies, either ZnSn(OH)(6) and SnO(2) serial enrichment or binary-component SnO(2)-ZnSn(OH)(6) enrichment in a single run, were proposed to enhance multi-phosphopeptide enrichment and to significantly improve global phosphopeptide detection.