Dendritic Pt nanostructures were prepared through electrodeposition on a substrate Pt electrode by applying square-wave potential method. It has been found that the as-prepared dendritic Pt nanostructure exhibited enhanced IR absorption with an enhancement factor up to 10 folds for adsorbed CO species. Such an enhanced in-situ FTIR spectroscopy (FTIRS) has been applied in studies of reaction mechanism of ammonia electro-oxidation. From in-situ FTIR spectra recorded during ammonia electrooxidation, two characteristic IR bands at 1430 cm(-1) and between 1227 and 1250 cm(-1) were observed at low potential region (E < - 0.50 V vs. SCE), and are assigned to adsorbed NH2,ad and N2H4,ad, respectively. The assignment of the band between 1227 and 1250 cm(-1) has been also confirmed through studies by using isotopic (NH3)-N-15 - NaOH and NH3 - NaOH - D2O systems. Furthermore, in spectra collected at high electrode potential region (E > 0.10 V vs. SCE), two IR bands at 2231 cm(-1) and 1236 cm(-1) were observed and ascribed respectively to N2O and NO2- species, which are the ultimate oxidation products detected under present investigation conditions. In addition to in-situ FTIR spectroscopy, online electrochemical mass spectroscopy (OEMS) was used to detect volatile products. The clear OEMS signals of m/e = 30 and m/e = 46 measured at potentials above -0.5 V and -0.30 V, respectively, indicate the production of N-2 (IR inactive) and confirm the generation of N2O. Based on results of cyclic voltanrimetry, in-situ FTIRS and OEMS, the reaction mechanism is therefore elucidated with molecular details of intermediates and products involved in ammonia electrooxidation in alkaline solutions.