Ti4+-immobilized　hierarchically　porous　zirconium-organic　frameworks　(denoted　as　THZr-MOFs)　was　prepared　for　phosphopeptide　enrichment.　The　THZr-MOFs　showed　high　specific　surface　area　of　185.28　m(2)　g(-1),　wide　pore-size　distribution　of　3　similar　to　20　nm,　good　chemical　stability　and　excellent　hydrophilicity.　Introduction　of　hierarchical　pores　in　MOFs　not　only　facilitated　the　accessibility　of　phosphopeptides　to　the　internal　metal　affinity　sites　and　reduce　their　mass　transfer　resistance,　but　also　increased　the　exposure　sites　of　metal　affinity　interaction　and　binding　energies　of　Zr　and　Ti　elements.　Benefited　from　these　advantages,　the　THZr-MOFs　showed　high　adsorption　capacity　(79.8　mu　g　mg(-1))　towards　standard　phosphopeptide.　A　low　detection　limit　(0.05　fmol　mu　L-1)　and　high　enrichment　selectivity　(beta-casein/BSA　with　a　molar　ratio　of　1:5000)　were　also　obtained　by　MALDI-TOF　MS.　The　THZr-MOFs　were　applied　to　analyze　complex　samples　including　nonfat　milk,　human　serum,　and　HeLa　cell　lysate.　In　total,　1432　phosphopeptides　derived　from　762　phosphoproteins　were　identified　from　human　HeLa　cell　lysate.