It is significant for flotation deinking to study the interactions between the surfactants and ink and waste office paper fiber. The adsorption of the surfactants in waste office paper recycling was investigated in this paper. Two common anion surfactants Sodium Dodecylbenzenesulfonate (SDBS) and Sodium Perfluorooctanoate (SPFO) and two typical substances hydrophobic carbon black (ink pigment) and hydrophilic office waste paper fiber were used to study their adsorption performance in flotation deinking. Meanwhile, calcium was added into surfactants to further explore the binding between calcium and surfactants, and its effects on the adsorption to the surface of carbon black and waste paper fiber. The results showed that when no calcium was added, the adsorption density of SDBS or SPFO on the surface of carbon black or paper fiber increased with the rise of SDBS or SPFO equilibrium concentration. And at sufficiently high surfactant concentrations, SPFO adsorbed bilayerly onro both paper fiber and carbon black, and also did SDBS on paper fiber. But SDBS showed monolayer adsorption on the surface of carbon black. When calcium was added to the surfactant solution, the adsorption of SDBS or SPFO on the surface of carbon black increased with the increase of calcium ion concentration. The maximum adsorption density was higher than that of SDBS at pH 9. The adsorption of SPFO on paper fiber showed the calcium rejection effect. The adsorption of SDBS on carbon black had nothing to do with pH value. Calcium was an effective catalyst in deinking of office waste paper, which could produce a synergistic effect with anionic surfactants to improve deinking effect.