Kinetic studies for the azo‐coupling reactions of 3‐ethoxythiophene 1 with a series of 4‐X‐substituted diazonium cations 2a‐e (X = OCH3, CH3, H, Cl, and NO2) have been investigated in acetonitrile at 20°C. The second‐order rate constants have been employed to determine the nucleophilicity parameters N and s of the thiophene 1 according the Mayr equation. Thus, the nucleophile‐specific parameters N and s of thiophene 1 have been derived and compared with the reactivities of other C‐nucleophiles in acetonitrile (pyrroles, furan, indoles, etc.). The Yukawa–Tsuno plot resulted in an excellent correlation (R2 = 0.9980) with an r value of 0.89, suggesting that the nonlinear Hammett plot observed in the present work is due to resonance demand of the π–electron donor substituent of on the –N2+ moiety. Importantly, using the concept of global electrophilicity (ω) proposed by Parr, we successfully predict the electrophilicity parameters E of seven substituted diazonium cations whose experimental data are available.