In this study, we present a detailed analysis of trapping characteristics at the AlxGa1-xN/GaN interface of AlxGa1-xN/GaN high-electron-mobility transistors (HEMTs) with reliability assessments, demonstrating how the composition of the Al in the AlxGa1-xN barrier impacts the performance of the device. Reliability instability assessment in two different AlxGa1-xN/GaN HEMTs [x = 0.25, 0.45] using a single-pulse ID-VD characterization technique revealed higher drain-current degradation (∆ID) with pulse time for Al0.45Ga0.55N/GaN devices which correlates to the fast-transient charge-trapping in the defect sites near the interface of AlxGa1-xN/GaN. Constant voltage stress (CVS) measurement was used to analyze the charge-trapping phenomena of the channel carriers for long-term reliability testing. Al0.45Ga0.55N/GaN devices exhibited higher-threshold voltage shifting (∆VT) caused by stress electric fields, verifying the interfacial deterioration phenomenon. Defect sites near the interface of the AlGaN barrier responded to the stress electric fields and captured channel electrons-resulting in these charging effects that could be partially reversed using recovery voltages. The quantitative extraction of volume trap density (Nt) using 1/f low-frequency noise characterizations unveiled a 40% reduced Nt for the Al0.25Ga0.75N/GaN device, further verifying the higher trapping phenomena in the Al0.45Ga0.55N barrier caused by the rougher Al0.45Ga0.55N/GaN interface.