Colour modification of tooth enamel has proven successful, but it is unclear how various bleaching applications affect micro-structural integrity of the whitened enamel. To investigate the internal structural integrity of human intact tooth enamel with the application of two commonly used whitening regimes (in-office power bleaching with 35% hydrogen peroxide and home bleaching with 10% carbamide peroxide), evaluations were performed on teeth of identical colour classification. After the bleaching applications, the enamel mineral density was quantified and visualised with micro-computed tomography. The micro-structural differences between the whitened tooth enamel samples were distinctive, though the colour parameter changes within the samples were equivalent. Home bleaching achieved colour modification by demineralisation, whereas in-office bleaching depended on redistribution of the minerals after treatment and subsequent enhanced mineralisation.