Herein, we demonstrated the first nickel-catalyzed double dehydrogenative condensation of secondary alcohols and β-amino alcohols in one-pot operation to the pyrrole derivatives. A series of 2,5 and 2,3,5-substituted pyrroles were obtained in up to 83% yield, releasing water and hydrogen gas as by-products. Initial mechanistic studies including defined Ni-catalysts, deuterium labeling experiments, quantitative determination of hydrogen gas evaluation and detection of water generation in the reaction mixture were performed.