The characteristic variation of heating coefficients (k = ΔT/ΔP°C/W) of Pt(H)–Ni electrolytic system with K2CO3 and Na2CO3 solutions was studied in both situations of electric and electrolytic heating, respectively. The results in equilibrium revealed that there was an obvious difference of k in electrolytic-heating (Δk ≈ 30°C/W, kK2CO3 > kNa2CO3) between these two systems, whereas there was a little difference of k in electric heating (Δk ≈ 2°C/W, kK2CO3 < kNa2CO3 between them. “Excess heat” of about 2.5 × 104J was produced during electrolysis of K2CO3 solution over 1 day of electrolysis. The differences of K2CO3 solution after electrolysis in the potential of hydrogen value (ΔpH = 0.15) and in absorbency (ΔA = 0.108) implied that some new Ca2+ might have formed in the electrolytic system.