The synthesis, crystal structure determination, magnetic properties and bonding interaction analysis of a novel 3d transition-metal complex, [CrBr2(NCCH3)4](Br3), are reported. Single-crystal X-ray diffraction results show that [CrBr2(NCCH3)4](Br3) crystallizes in space group C2/m (No. 12) with a symmetric tribromide anion and the powder X-ray diffraction results show the high purity of the material specimen. X-ray photoelectron studies with a combination of magnetic measurements demonstrate that Cr adopts the 3+ oxidation state. Based on the Curie–Weiss analysis of magnetic susceptibility data, the Néel temperature is found to be around 2.2 K and the effective moment (μeff) of Cr3+ in [CrBr2(NCCH3)4](Br3) is ∼3.8 µB, which agrees with the theoretical value for Cr3+. The direct current magnetic susceptibility of the molecule shows a broad maximum at ∼2.3 K, which is consistent with the theoretical Néel temperature. The maximum temperature, however, shows no clear frequency dependence. Combined with the observed upturn in heat capacity below 2.3 K and the corresponding field dependence, it is speculated that the low-temperature magnetic feature of a broad transition in [CrBr2(NCCH3)4](Br3) could originate from a crossover from high spin to low spin for the split d orbital level low-lying states rather than a short-range ordering solely; this is also supported by the molecular orbital diagram obtained from theoretical calculations.