The (1–x)NaNO2 + xBaTiO3 composites of two compositions (x = 0.05 and 0.1) have been studied by powder neutron diffraction and broadband dielectric spectroscopy (frequency region 10–1–107 Hz). The temperature dependences of the ferroelectric order parameter of NaNO2 in the composites and pure NaNO2 have been measured. The frequency dependences of the real and imaginary parts of the permittivities of the composites and pure NaNO2 have been analyzed in the temperature range 25–187°C. The anomaly of the dielectric response observed at T ~ 147°C is assumed to be related to the processes of accumulation and “resolution” of charges at the BaTiO3 particle boundaries.