Ex: NaCl molecule will dissociate at higher temperatures, but on electrolysis it will decompose easily.
Using electricity the non-spontaneous reactions can also takes place easily.
Ex: Water cannot be dissociated easily by supplying but when electricity it can dissociated into its elements.
2H2O→ 2H2 + O2
2NaCl → 2Na (at Cathode)+ Cl2 (at anode)
2AlCl3 → 2Al (at Cathode) + 3 Cl2 (at anode)