HRMS/MS library for screening food safety needs more than compound coverage as proof of operational worth. Robust collision-energy, unresolved workload by chemical class, visibility at repository level, and ion form–level agreement for compounds found in external libraries are other necessary factors. This research evaluates a positive-ion HRMS/MS library of food-toxicants containing 1001 compounds and 6993 manually curated spectra. The numerical information available consists of six normalized-collision-energy annotation rates, five chemical-class strata, repository-visibility numbers, and ten compound-level modified-cosine scores. NCE30 generated the highest single correct-annotation rate of 63.4%, but the use of the library would be much more justified by the use of an NCE15-NCE60 collision energy shelf having an average annotation rate of 62.73%, which is 2.63 percentage points higher than that of an NCE75-NCE90 shelf. Pesticides make up the greatest unresolved workload share of 41.2%, while organic contaminants have the greatest scarcity-adjusted vulnerability despite being just 5.3% of compounds. The comparison with public repositories shows that there are 216 compounds, 21.6% of the library, lacking in four repositories; cleaned GNPS and MS2Query planar InChIKey overlap differ in just 16 compounds. The ten-entry compound comparison has two concordant, three provisional, and five discordant entries; mean modified cosine score is 0.43, and normalized triage entropy is 0.94. These figures provide routine-use value for the NCE15-NCE60 collision energy shelf and concordant shared entries, while pointing to the need to curate pesticides, retain organic contaminant entries, and distribute 216 public-repository absent compounds.