In 1862 Payer had started exploratory tours of the Tyrolean Alps and the High Tauern range in his free time. After 1864 he explored the Adamello-Presanella Group and the Ortler Alps, making more than 60 first ascents. In 1864 he was, with his guide Giovanni Caturani, the first to climb Adamello (3,554 m) and missed making the first ascent of the Presanella (3,558 m) by just three weeks. All his explorations in the Ortler massif (from 1865 to 1868) were guided by from Sulden. Together, often accompanied by a porter, they ascended almost all significant unclimbed summits, including the Hoher Angelus (3,521 m), Vertainspitze (3,545 m), Palon de la Mare (3,703 m), Monte Zebru (3,735), and Monte Cevedale (3,769 m). Their new approach to the Ortler (3,905 m) became the normal route of ascent ever since.