t-Butyl 4-alkyl-1H-pyrrole-2-carboxylates were oxidized with DDQ in the presence of MeOH at the alpha-position of the alkyl substituent at the C-4 position regioselectively to afford 4-acylpyrrole derivatives. On the other hand, treatment of the pyrroles with DDQ in the presence of AcOH furnished the corresponding 4-(1-acetoxyalkyl)pyrroles. The resulting 4-(acetoxymethyl)pyrrole reacted with various nucleophiles to afford the functionalized pyrrole derivatives in good yields.