Four new polyphenols, loddigesiinols G-J (compounds 1-4) and a known compound, crepidatuol B (5), were isolated from the stems of Dendrobium loddigesii that have long been used in Traditional Chinese Medicine and have recently been used to treat type 2 diabetes. Compounds 1-5 structures were elucidated based on spectroscopic analysis. The absolute configurations of compounds 1-4 were determined using theoretical calculations of electronic circular dichroism (ECD), and the absolute configuration of compound 5 was determined by a comparison of the experimental ECD spectra and the literature data. Compounds 1-5 are strong inhibitors of α-glucosidase, with IC50 values of 16.7, 10.9, 2.7, 3.2, and 18.9 μM, respectively. Their activities were significantly stronger than trans-resveratrol as a positive control (IC50 values of 27.9 μM).