Total dissolved nitrogen (TDN) is an important parameter for assessing the nutrient cycling and status of natural waters. The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water. The TDN in various systems has been largely documented, and the concentrations of TDN are usually obtained using high-temperature catalytic ( HTC) or persulfate oxidation (PO). However, the accuracy of these methods and their suitability for all types of natural waters are still unclear. To explore both methods in-depth, assorted samples were tested, including eight solutions composed of nitrogen-containing compounds (3 dissolved inorganic nitrogen fractions: NO3-, NO2 and NH4I; 5 organic compounds: EDTA-2Na, vitamin B1, vitamin B12, amino acids, and urea) and 105 natural waters which were collected from an open ocean (Northwest Pacific Ocean, 28), a marginal sea (Yellow Sea, 34), an estuary (Huanghe River mouth, 31), rivers (Huanghe River, 4; Licun River, 4), and precipitations (4 samples). The results showed that heterocycles and molecular dimensions had certain effects on the oxidation efficiency of the PO method but had little effect on HTC. There was no significant difference between the two methods for natural waters, but HTC was more suitable for deep-sea samples with low TDN concentrations (less than 10 mu mol/L) and low organic activity. Overall, HTC has a relatively simple measurement process, a high degree of automation, and low error. Therefore, HTC can be recommended to determine the TDN of samples in freshwater and seawater.