The electroreductive coupling of phthalimides with α,β-unsaturated carbonyl compounds in the presence of TMSCl and successive treatment of the electrochemically coupled products with TFA gave two types of rearranged products, 3- and 2-substituted 4-aminonaphthalen-1-ols. The substituent (R) on the nitrogen atom of phthalimides determined which type of 4-aminonaphthalen-1-ol was preferentially formed. Bulky and less bulky N substituents selectively afforded 3- and 2-substituted 4-aminonaphthalen-1-ols, respectively. It was presumed by the density functional theory calculations for the acid-catalyzed rearrangement of silyl ketene acetals produced by the electroreductive coupling that the rearranged product selectivity depends on whether O or N protonation of the amide group of the silyl ketene acetals occurs more rapidly.