The dielectric constant ϵ and the dielectric loss tan δ of (p‐Cl‐anilinium)2MnCl4 as function of temperatures (280 to 370 K) and frequencies (10 Hz to 10 kHz) are investigated. The electric conductivity σ is measured as function of temperature and frequency. Magnetic susceptibility versus temperature and DTA measurements are also performed. The results show an order—disorder structural phase transition at Ttr = (345 ± 3) K. Above the transition, conductivity is due to space‐charge polarization, while below it conduction is mainly due to the hopping mechanisms.

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