A novel ultra-small hydrazone-linked covalent organic polymer (UHCOP) was synthesized based on the Schiff-base reaction between 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde and 1,4-benzenedicarbohydrazide at room temperature and utilized as a sensitive fluorescent sensor for rapid (<2 min) and selective detection of Fe3+ in aqueous solution. The prepared UHCOP displayed ultra-small size with the diameter of 7.98 ± 0.97 nm and gave a stable fluorescent emission at 510 nm. UHCOP exhibited good sensitivity and highly selectivity towards Fe3+. The coordination interaction between UHCOP and Fe3+ resulted in the obviously aggregation-caused quenching response of UHCOP. The linear range was from 5.0 μM to 1.4 mM (R2 = 0.999) with the detection limit of 2.5 μM. Finally, UHCOP has been successfully applied in the detection of Fe3+ in real water samples, proving the fabricated UHCOP is promising as a sensitive fluorescent sensor for selective detection of Fe3+ in aqueous solution.