Ten room temperature protic ionic liquids (RTPILs) have been prepared from low-molecular-weight Brønsted acids and amines with high purity and minimal water content, and their electrochemical characteristics determined using cyclic, microelectrode, and rotating disk electrode voltammetries. Potential windows of the 10 RTPILs were established at glassy carbon, gold, and platinum electrodes, where the largest potential window is generally observed with glassy carbon electrodes. The two IUPAC recommended internal potential reference systems, ferrocene/ferrocenium and cobaltocenium/cobaltocene, were determined for the 10 RTPILs, and their merits as well as limitations are discussed. Other electrochemical properties such as mass transport and double layer capacitances were also investigated. The potential applications of these RTPILs as electrolytes for electrochemical energy devices were discussed, and two novel applications using PILs for metal deposition and water electrolysis were demonstrated.