Tribochemical silica coating (TSC) is commonly used to pretreat zirconia surfaces prior to luting. Although many studies demonstrate an adhesion-promoting effect of TSC on zirconia, its actual interaction mechanism has not been fully elucidated. We therefore characterized the ultrastructure of TSC-treated zirconia and tested shear-bond strength. STEM/EDS disclosed a micro-roughened zirconia surface partially covered with fused Al and Si, while residual unfused silica particles could also still be detected. TSC-treated zirconia having received the solely silane primer exhibited a significantly lower shear-bond strength than zirconia on which the combined 10-MDP/silane primer was applied. SEM fracture analysis revealed residual silica particles on both the zirconia and cement sides. Correlative ultrastructural and chemical surface characterization revealed that TSC deposited an inhomogeneous silica layer on the zirconia surface, which explains why the solely silane coupling agent was less effective than the combined 10-MDP/silane ceramic primer for bonding to zirconia pretreated by TSC.