Selected hexasubstituted benzenes containing one or two nitro groups and chlorine atoms or methyl groups have been studied in the solid state by means of dielectric, differential scanning calorimetry (DSC), X-ray and Raman techniques. Unknown phase transitions at 223 and 412 K were found in pentachloronitrobenzene (PCNB), and the existence of a rotational phase above 223 K was confirmed with the help of dielectric measurements. In the case of 1,3-dinitrotetramethylbenzene (1,3-DNTMB) and 1,3-dinitrotetrachlorobenzene (1,3-DNTCB) permittivity dispersion in a low-frequency range has not been detected which was interpreted as a lack of rotatory phases in these compounds. No rotational phase in compounds with the angle between the aromatic ring and nitro group planes equal or close to 90° has been found. The crystal structure of 1,3-DNTCB was determined. 1,3-DNTCB crystallizes in P2 1 /c space group with Z = 4 molecules in a unit cell. DSC data for the studied crystals are quoted for the temperatures from 305 K to the melting point. Low-frequency Raman spectra of the studied compounds are presented and discussed.