A combination of nitrogen isotope analysis and X-ray photoelectron spectroscopy techniques was used to characterize nitrogen isotopic compositions and organic nitrogen forms in a total of 11 coal samples from China. A range of delta N-15 values between -2.9 parts per thousand and +3.6 parts per thousand was observed in all coals, and the N-5 peak is predominant. The results show that a correlation exists between the delta N-15 value and the proportions of the N-S peak and the sum of the N-6 and N-Q peaks. This suggests that the nitrogen isotopic composition of coal may be controlled by the distribution of nitrogen forms. The pyridinic-structure nitrogen is enriched in N-15 compared with the pyrrolic-structure nitrogen.