When existing at emulsion interface and continuous phase, dispersibility of water-soluble flexible polymer chains has obvious effect on rheology and dielectric properties of whole emulsion. CNF Pickering emulsion is a good system to research these properties with respect to their microscopic phase structure, dielectric and rheological properties by using cellulose nanofibers (CNF) as water-soluble Pickering emulsifier, liquid Paraffin as oil phase and DDAB as a cationic auxiliary surfactant. The CNF- and DDAB-contents were systematically varied while the water to paraffin oil ratio remained constant to discern the influence of the Pickering emulsifiers. Polarized optical microscopic images revealed that the droplets have tendency to become smaller size for higher CNF content, but bigger size for higher DDAB content, which was proved by the fluorescent analysis for CNF dispersibility with varying DDAB content. The dielectric damping exhibits a minimum, whose value decreases with increasing DDAB- and CNF-content. Increasing the DDAB-content promotes solubilization of CNFs in the aqueous phase and will increase the overall viscosity and yield points. Similarly, a higher CNF-content leads to a higher viscosity and yield point, but at high DDAB-contents the viscosity function exhibits an S-shape at intermediate CNF-content. To evaluate the results further they were compared with CNF-dispersions (without oil-phase), which showed a surfactant effect slightly on maximum stress but strongly on yield stress τy, indicating DDAB can promote the formation of CNF network rather than the viscosity of whole system.