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Abstract Background The aim of this prospective cohort study is to substantiate the added value of diffusion-weighted magnetic resonance imaging (DW-MRI) over conventional MRI assessment in the differentiation between locoregional recurrence/residual tumour and post-treatment benign changes in patients with non-lymphoid head and neck malignancies. Thirty adult patients, each with a suspicious lesion on post-treatment imaging scans at the primary site of a previously treated non-lymphoid head and neck malignancy, were evaluated by MRI and diffusion-weighted imaging (DWI). The apparent diffusion coefficient (ADC) values of the lesions were calculated. Results Diffusion-weighted MRI yielded an accuracy of 90%, a sensitivity of 88.9%, a specificity of 91.7%, a positive predictive value of 94.1% and a negative predictive value of 84.6%. The mean ADC value of the lesions was lower in the “locoregional recurrence/residual tumour” group (1.08 × 10−3 mm2/s) compared to the “post-treatment benign changes” group (1.95 × 10−3 mm2/s); P < 0.001. An ADC cutoff value of 1.43 × 10−3 mm2/s achieved the same accuracy as the visual assessment by DW-MRI. Conclusion Incorporating the DWI sequence into the post-treatment imaging assessment protocol brings a substantial added value to conventional MRI assessment in patients with non-lymphoid head and neck malignancies. This valuable merit of DW-MRI can help avoid or, at least, largely minimize unnecessary or unfeasible tissue sampling. An ADC cutoff value of 1.43 × 10−3 mm2/s can also be utilized to aid in the assessment process.