The number of species in <i>Aspergillus</i> section <i>Flavi</i> has recently increased to 36 and includes some of the most important and well-known species in the genus <i>Aspergillus</i>. Numerous secondary metabolites, especially mycotoxins, have been reported from species such as <i>A. flavus</i>; however many of the more recently described species are less studied from a chemical point of view. This paper describes the use of MS/MS-based molecular networking to investigate the metabolome of <i>A. caelatus</i> leading to the discovery of several new diketopiperazine dimers and aspergillicins. An MS-guided isolation procedure yielded six new compounds, including asperazines D-H (<b>1</b>-<b>5</b>) and aspergillicin H (<b>6</b>). Asperazines G and H are artifacts derived from asperazines E and F formed during the separation process by formic acid. Two known compounds, aspergillicins A and C (<b>7</b> and <b>8</b>), were isolated from the same strain. Structures were elucidated by analyzing their HR-MS/MS and NMR spectroscopic data. The absolute configuration of asperazines D-F and aspergillicin H were deduced from the combination of NMR, Marfey's method, and ECD analyses.