The most difficult diagnostic challenge in neck imaging is the differentiation between benign and malignant neoplasms. The purpose of this work was to study the role of the ADC (apparent diffusion coefficient) value in discriminating benign from malignant neck neoplastic lesions. The study was conducted on 53 patients with different neck pathologies (35 malignant and 18 benign/inflammatory). In all of the subjects, conventional MRI (magnetic resonance imaging) sequences were performed apart from DWI (diffusion-weighted imaging). The mean ADC values in the benign and malignant groups were compared using the Mann-Whitney test. The ADCs of malignant lesions (mean 0.86 ± 0.28) were significantly lower than the benign lesions (mean 1.43 ± 0.57), and the mean ADC values of the inflammatory lesions (1.19 ± 0.75) were significantly lower than those of the benign lesions. The cutoff value of 1.1 mm2/s effectively differentiated benign and malignant lesions with a 97.14% sensitivity, a 77.78% specificity, and an 86.2% accuracy. There were also statistically significant differences between the ADC values of different malignant tumors of the neck (p, 0.001). NHL (0.59 ± 0.09) revealed significantly lower ADC values than SCC (0.93 ± 0.15). An ADC cutoff point of 0.7 mm2/s was the best for differentiating NHL (non-Hodgkin lymphoma) from SCC (squamous cell carcinoma); it provided a diagnostic ability of 100.0% sensitivity and 89.47% specificity. ADC mapping may be an effective MRI tool for the differentiation of benign and inflammatory lesions from malignant tumors in the neck.