 Electrochemical study of several 5-(azulen-1-ylmethylene)-2,2-dimethyl-1,3-dioxane-4,6-diones was performed by cyclic and differential pulse voltammetry to evaluate the influence of donor and acceptor substituents on their electrochemical behavior. The number and characteristics of the redox processes for each compound were established. The electrochemical parameters have been correlated with ionization potentials and lowest unoccupied molecular orbital energies evaluated through computational methods for the azulene moiety grafted with different functional groups.