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An I 2 -mediated N-GQDs was developed to fluorescent probes for S 2 O 3 2− and oxidative compounds such as H 2 O 2 via iodimetry reaction oriented strategy. This nanoprobe with the excellent selectivity and sensitivity (93 pM) has been successfully applied in biological fluids and living cells for S 2 O 3 2−. [Display omitted] • a I 2 -mediated N-GQDs nanocomposite as a fluorescence probe for S 2 O 3 2− and oxidative compounds. • S 2 O 3 2− detection by I 2 -mediated N-GQDs via "iodimetry reaction oriented" strategy. • I 2 -mediated N-GQDs exhibiting the high selectivity and the super low LOD of 93 pM towards S 2 O 3 2−. • successful detection of S 2 O 3 2− in real water samples, biological fluids, and living cells. Owing to the huge threat to human health and environment from thiosulfate anion (S 2 O 3 2−) widely used in various fields, the development of an effective detection method for S 2 O 3 2− is urgently desired. Herein, we developed an iodine (I 2) mediated nitrogen-doped graphene quantum dots (I 2 -mediated N-GQDs) as a fluorescence "off-on" probe for S 2 O 3 2− by iodimetry reaction oriented strategy. Firstly, I 2 interacted with N-GQDs to form non-fluorescent N-GQDs/I 2 complex due to the inner filter effect (IFE). In the presence of S 2 O 3 2−, the iodimetry reaction between I 2 and S 2 O 3 2− disintegrated N-GQDs/I 2 complex and re-switched on the quenched photoluminscence of N-GQDs. The I 2 -mediated N-GQDs nanoprobe with a limit of detection down to 93 pM has been successfully used to sense S 2 O 3 2- in biological fluids and living cells. Moreover, the I 2 -mediated N-GQDs/S 2 O 3 2− nanoplatform could further detect oxidative compounds such as hydrogen dioxide, dichromate, permanganate, iron ion (III), copper ion (II), and cerium ion (IV). [ABSTRACT FROM AUTHOR]