Indopexines A (1) and B (2), two prenylated isoindoline alkaloids, were isolated from Aspergillus sp. TJ507. Their structures were determined by extensive spectroscopic analysis, CASE algorithms, quantum 1H and 13C NMR DP4+, and electronic circular dichroism calculations. Structurally, 1 was the first examples of isoindoline alkaloids bearing a 6/5/5/6 ring based on the 2-oxa-10-azatetracyclo-[7.7.0.01,12.03,8]cetane core, while 2 featured an 5,20-bioxa-1-azapencyclo-[10.7.1.01,12.06,11.013,18]lcosane moiety. Furthermore, 1 displayed an inhibitory effect toward triple-negative breast cancer cells through the Rap1/PI3K/AKT signaling pathway.