For mass spectrometry (MS)-based phosphoproteomics studies, sample pretreatment is an essential step for efficient identification of lowabundance phosphopeptides. Herein, a cobalt phthalocyanine-modified magnetic metal−organic framework (MOF) (Fe 3 O 4 @MIL-101-CoPc) was prepared and applied to enrich phosphopeptides before MS analysis. Fe 3 O 4 @ MIL-101-CoPc exhibited an excellent magnetic response (74.98 emu g −1 ) and good hydrophilicity (7.75°), which were favorable for the enrichment. Fe 3 O 4 @ MIL-101-CoPc showed good enrichment performance with high selectivity (1:1:5000), sensitivity (0.1 fmol), reusability (10 circles), and recovery (91.3%). Additionally, the Fe 3 O 4 @MIL-101-CoPc-based MS method was able to successfully detect 827 phosphopeptides from the A549 cell lysate, demonstrating a high enrichment efficiency (89.3%). This study promotes the application of postfunctionalized MOFs for phosphoproteomics analysis.