The variation of linkage positions in ginsenosides leads to diverse pharmacological efficiencies. The hydrolysis and transglycosylation properties of glycosyl hydrolase family enzymes have a great impact on the synthesis of novel and structurally diversified compounds. In this study, six ginsenoside Rg(1)-alpha-glucosides were found to be synthesized from the reaction mixture of maltose as a donor and ginsenoside Rg(1) as a sugar acceptor in the presence of rat small intestinal homogenates, which exhibit high alpha-glucosidase activities. The individual compounds were purified and were identified by spectroscopy (HPLC-MS, H-1-NMR, and C-13-NMR) as 6-O-[alpha-D-glcp-(1 -> 4)-beta-D-glcp]-20-O-(beta-D-glcp)-20(S)-protopanaxatriol, 6-O-beta-D-glcp-20-O-[alpha-D-glcp-(1 -> 6)-(beta-D-glcp)]-20(S)-protopanaxatriol, 6-O-beta-D-glcp-20O-[alpha-D-glcp-(1 -> 4)-(beta-D-glcp)]-20(S)-protopanaxatriol, 6-O-[alpha-D-glcp-(1 -> 6)-beta-D-glcp]-20O-(beta-glcp)-20(S)-protopanaxatriol, 6-O-[alpha-D-glcp-(1 -> 3)-beta-D-glcp]-20-O-(beta-D-glcp)-20(S)-protopanaxatriol, and 6-O-beta-D-glcp-20-O-[alpha-D-glcp-(1 -> 3)-(beta-D-glcp)]-20(S)-protopanaxatriol. Among these six, 6-O-beta-D-glcp-20-O-alpha-D-glcp-(1 -> 6)-(beta-D-glcp)-20(S)-protopanaxatriol and 6-O-alpha-D-glcp-(1 -> 6)-beta-D-glcp-20-O-(beta-D-glcp)-20(S)-protopanaxatriol are considered to be novel compounds of alpha-ginsenosidal saponins which pharmacological activities should be further characterized. This is the first report on the enzymatic elaboration of ginsenoside Rg(1) derivatives using rat intestinal homogenates. To the best of our knowledge, it is also the first to reveal the sixth and 20th positions of an unusual alpha-D-glucopyranosyl-(1 -> 6)-beta-D-glucopyranosyl sugar chain with 20(S)-protopanaxatriol saponins in Panax ginseng Mayer.