Disulfide zirconium (ZrS2) is a two-dimensional (2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties. However, mass production of high quality of ZrS2 nanosheets to realize their practical application remains a challenge. Here, we have successfully exfoliated the bulk ZrS2 powder with the thickness of micron into single and few-layer nanosheets through liquid-phase exfoliation in N-methylpyrrolidone (NMP) assisted via aliphatic amines as intercalators. It is found that the exfoliation yield is as high as 27.3%, which is the record value for the exfoliation of ZrS2 nanosheets from bulk ZrS2 powder, and 77.1% of ZrS2 nanosheets are 2–3 layers. The molecular geometric size and aliphatic amine basicity have important impact on the exfoliation. Furthermore, the ZrS2 nanosheets have been used as catalyst in the electrocatalytic dinitrogen reduction with the NH3 yield of 57.75 μg h−1 mgcat.−1, which is twice that by ZrS2 nanofibers reported in literature and three times that by the bulk ZrS2 powder. Therefore, the liquid phase exfoliation strategy reported here has great potential in mass production of ZrS2 nanosheets for high activity electrocatalysis.