We apply the desorption mass spectrometry (DMS) technique and analyze the desorbed Sb species in-situ during MBE growth of mixed As/Sb heterostructures. We demonstrate how DMS is useful in pre-growth calibration of the V/III ratio, the group-III ratio, as well as the Sb-content in quaternary or quinary mixed As/Sb alloys. We also apply DMS to the digital alloy growth method. For demonstration purposes, we start with an un-calibrated MBE system, use the DMS technique to calibrate all of the previously undetermined MBE parameters and grow a ~3.3µm diode laser heterostructure in only one attempt. The results demonstrate that the DMS technique will allow the MBE to quickly converge toward a set of acceptable growth parameters without the need for ex-situ calibration of alloy composition.