Deinking is an important step in recycling of waste paper and flotation is commonly used in this process. By studying the interaction between added surfactant and the solid surfaces of ink pigment and pulp, the fundamental mechanism of flotation deinking can be better understood. In this work, the adsorption of two anionic surfactants (sodium dodecyl sulfate, SDS and sodium octanoate, C8) on both a model ink (hydrophobic carbon black) and a model fiber (hydrophilic office paper) was studied. The effect of pH on the SDS adsorption and the co-adsorption of calcium and surfactant on both surfaces also were investigated. The SDS adsorbs on carbon black as a tail-down monolayer (hemimicelle) while on paper fiber as a head-down, head-out bilayer (admicelle). The C8 forms admicelles on both carbon black and paper fiber indicating the stronger interaction of the carboxylate group with the carbon surface than the surfactant sulfate group, causing the C8 to adsorb at higher levels than SDS on carbon black. This helps explain why soaps are used widely as the surfactant in flotation deinking operations. Calcium causes surfactant adsorption to increase on carbon black as it adsorbs between negatively charge surface sites and the anionic head group of the surfactant (bridging) especially at low surfactant levels while not enhancing surfactant adsorption on paper fiber, explaining its activation effect in deinking processes. At high surfactant loadings, increasing surfactant concentration can cause calcium adsorption to decrease (calcium exclusion effect), probably due to covering up of negative adsorption sites on the surface.