The photo differential scanning calorimetry (photo-DSC) is an appropriate method to characterize photopolymers used in additive manufacturing (AM). Important process parameters such as optimal ultraviolet (UV) exposure time and reaction heat can be attained by this method. However, achieving reliable and meaningful results from photo-DSC experiments requires careful sample preparation, i.e. the selection of a suitable sample shape, sample mass and sample holder (crucible). The sample shapes drop and spread with 1.0 mg and 2.8 mg sample masses were investigated in this study. Three different times from sample preparation until the start of the measurement (0, 4 and 7 h) were tested, in order to investigate different surface effects such as oxygen-diffusion, prior UV-curing through ambient radiation and evaporation of volatile components. While the 1.0 mg spread sample shape offers the thinnest film thickness (40 μm) and thus the closest comparability to high resolution print jobs, the 2.8 mg drop shape offers a more robust sample preparation with minimized surface effects. To further reduce time-dependent surface effects, this study shows how a preexisting test protocol was shortened from 42 min to 24 min without losing measuring accuracy. Furthermore, to reduce evaporation, different covers were placed on different crucibles, which were tested over time in the device’s automated sample changer (ASC) that enables automated and consecutive measurements. The combination of a cold pressed 85 μL crucible covered with a 300 μL Al2O3 crucible, which is removed shortly before the actual measurement, provides the best sample preparation for the ASC since mass loss remains below 1% for up to 10 h. Finally, two two-part resin systems, namely a methacrylate-urethane and an acrylate-epoxy based resin that are used in Digital Light Synthesis (DLS) are characterized part by part as well as in mixed state. Together with the investigation of different temperatures and atmospheres, it was possible to identify not only the part with the photoinitiator and the type of system (radical or cationic), but also a difference between methacrylates and acrylates with the aid of the photo-DSC method. Display omitted •The 1.0 mg spread sample shape has shortest times to peak.•The 2.8 mg drop sample shape is more robust towards time-dependent surface effects.•EPX 82 follows a radical not a cationic or hybrid reaction system.•The reaction heat of EPX 82 is almost twice as much compared to RPU 70.•Sample preparation for reduced mass loss with the ASC of the DSC is presented.