p-Phenylenediamine (p-PDA) is a toxic constituent utilized in textiles, black henna tattoos, hair dyes, pesticides, polymers etc. The metabolites (quinone etc.) produced by p-PDA cause mutagenic and carcinogenic effects in humans as it is quickly absorbed by the blood after oral intake or intake through the skin. Therefore, the literature reports several conventional approaches (such as colorimetry and chromatography) and electrochemical/voltammetric approaches to determine and quantify p-PDA. Amongst them, the electrochemical approach is the most preferable because of the short analysis time, cost-effectiveness, ease of use, ease of miniaturization etc. This is the first review to discuss the sources and toxic effects, and make a comparison between conventional and electrochemical methods for the determination and quantification of p-PDA in analytical samples.