In this study, fluorescent red-carbon quantum dots (R-CQDs) with an ultrahigh fluorescence quantum yield of 45% were rapidly and easily synthesized by thermal pyrolysis of 2,5-diaminotoluene sulfate and 4-hydroxyethylpiperazineethanesulfonic acid using a one-step microwave-assisted hydrothermal approach. R-CQDs possessed the excitation-independent fluorescence property with the optimal emission peak at 607 nm under the excitation wavelength of 585 nm. R-CQDs exhibited excellent fluorescence stability under extremely harsh conditions in a pH range of 2-11, high ionic strength (1.8 M of NaCl), and long UV light irradiation time (160 min). The fluorescence quantum yield of these R-CQDs was as high as 45%, implying their preferable application in chemosensors and biological analysis. Because Fe3+ ion bound with R-CQDs and statically quenched the fluorescence of R-CQDs, the fluorescence intensity of R-CQDs was recovered after the addition of ascorbic acid (AA) via its redox reaction with Fe3+ ion. R-CQDs were developed as highly sensitive fluorescent on-off-on probes for sequentially sensing Fe3+ ions and AA. Under the optimal experimental conditions, the linear range for Fe3+ ion detection was 1-70 μM with a detection limit of 0.28 μM, and the linear range for AA detection was 1-50 μM with a detection limit of 0.42 μM. The successful detection of Fe3+ ions in authentic water samples and the successful sensing of AA in human body fluids and vitamin C tablets further proved the practical application prospects of this efficient strategy in the environmental protection and disease diagnosis fields.