Biological-material-functionalized porous monoliths were prepared with lactoferrin and beta-cyclodextrin via a click reaction. With the monolith as an extraction medium, a method combined with ICP-MS was developed for the determination of total gallium originating from metabolic residues of orally bioavailable gallium complexes with tris(8-quinolinolato)gallium (GaQ(3)) as a representative. The method exhibited favorable adsorption behaviors for gallium with high selectivity, low detection limit (2 ng L-1), and an enrichment factor of 29-fold with the sample throughput of 30 min(-1). The developed approach was validated by the analysis of gallium from GaQ(3) metabolic residues in a human cell line. Additionally, the practical applicability of this, method was evaluated by the determination of gallium in human blood and urine samples from cancer patients. Results illustrated that the prepared monolith had potential in Ga-based anticancer drug analysis in complex biological samples.