Nanostructured silicon nitride solids (NANO–SSNS) were investigated by x–ray photoelectron spectroscopy (XPS), electron spin resonance (ESR) and dielectric measurements. It is found that the dielectric constant of NANO–SSNS depends strongly on the measuring frequency, f. When f<100Hz, at room temperature it is forty times as much as that of conventional Si3N4. ESR measurements show that a large number of unbinding electrons exist in interfaces. This suggests that the NANO–SSNS possess strong polarity. The study on the bond properties indicates that a large number of unsaturated and dangling bonds exist in interfaces of NANO–SSNS.