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Abstract In this work, a comparative study of diamond films consisting of alternate microcrystalline (MCD) and nanocrystalline diamond (NCD) layers is conducted. Diamond films including monolayer, bilayer and multilayer diamond films are coated on cemented tungsten carbide (WC-Co) substrates by adopting a bias-enhanced hot filament chemical vapor deposition (HFCVD) technique. Tribological properties of the diamond films are evaluated by using a reciprocal tribometer without lubrication. Further milling tests are carried out to examine the cutting performances with sintered zirconia ceramics as workpiece comparatively. In friction test against zirconia ceramics, the monolayer NCD film shows the lowest friction coefficient (0.128) because of its smooth surface. Also, the bilayer diamond film with surface coating of NCD layer (MNCD) and both of the multilayer diamond films exhibit good friction property while the monolayer MCD film has the largest friction coefficient (0.292). The milling test demonstrates that the monolayer diamond (MCD and NCD) coated milling tools show poor tool life due to abrasive action of hard workpiece. Working life of all the bilayer and multilayer diamond coated tools is enhanced, but large area shedding of coatings appears after some milling passes except the multilayer diamond film with surface coating of NCD layer (MNMN-CD). The multilayer film (MNMN-CD) presents superior machining performance and its working life increases by 3–7.5 times compared with the monolayer diamond coated ones. Highlights • Diamond films with distinct multilayer structures are fabricated. • Multilayer diamond films are consisted of alternate MCD and NCD layers. • Multilayer diamond films exhibit good friction properties and low COF values. • Multilayer diamond films could improve the life of mills greatly. • Multilayer diamond coated mills show the best potential for zirconia machining. [ABSTRACT FROM AUTHOR]