Nicotinamide (NA) has been shown to have beneficial effects on several skin diseases such as tumor, acne vulgaris, photodamage, cellulite and atopic dermatitis. The purpose of this study was to develop a multiple emulsion and a microemulsion formulation as delivery systems for NA. A two-step process was used to prepare the W/O/W multiple emulsion. Optimum microemulsion formulation was selected by using construction of pseudo-ternary phase diagram. The physicochemical properties such as droplet size and viscosity measurements, stability studies were also evaluated. Ex-vivo permeation studies were performed with Franz-type diffusion cells and the samples were analysed by high performance liquid chromatography (HPLC). The permeation data showed that there was no significant difference between multiple emulsion and microemulsion (p > 0.05). Transepidermal water loss (TEWL) was also measured. As a result of TEWL studies, a slight increase of TEWL values was observed for microemulsion formulation on rat skin when compared with multiple emulsion and commercial formulation. The results suggested that microemulsion and multiple emulsion formulations could be new and alternative dosage forms for topical application of NA.