Passive and iontophoretic transport of fluoride from three fluoride sources, NaF, sodium monofluorophosphate (MFP), and SnF2 solutions, across bovine enamel was investigated to (1) determine the characteristics of the intrinsic barrier of enamel for ion transport, (2) examine the feasibility of iontophoretically enhanced transport of fluoride across enamel, and (3) identify the transport mechanisms involved in enamel iontophoresis. Conductivity experiments were performed with bovine enamel specimens in side-by-side diffusion cells to evaluate the electrical and barrier properties of the enamel with electrolytes of different ion sizes and under different ion concentrations and pH conditions in vitro. Transport experiments of the enamel were performed in the diffusion cells with the NaF, MFP, and SnF2 solutions. The conductivity results showed that the enamel specimens behaved as a neutral membrane or that of low pore charge density. Cathodal iontophoresis significantly enhanced the delivery of fluoride ions across the enamel from the solutions over passive transport, consistent with Nernst-Planck theory and the direct field effect (i.e., electrophoresis) as the dominant flux-enhancing mechanism. The enamel demonstrated significant transport hindrance for the ions, and the effective pore radii of the transport pathways in the enamel were found to be approximately 0.7-0.9 nm.