Ultra-high performance geopolymer concrete (UHPGC) is increasingly recognised as a promising construction material in protective engineering owing to its exceptional material strength and eco-friendly characteristics. However, there is currently limited research data on the behaviour of UHPGC under complex stress states, and the applicability of some common concrete dynamic constitutive models to UHPGC requires calibration and evaluation. This paper presents an experimental study on the triaxial compression (TXC) behaviour of UHPGC under varying confining pressures with a range of 0–40 MPa. The stress-strain curves under various confinement levels and failure patterns of UHPGC are discussed. The results indicate that the peak axial stress and toughness of UHPGC increase with higher confining pressure levels, but it still exhibits noticeable softening behaviour. Under uniaxial compression, UHPGC typically fails with inclined shear and axial tensile cracks, while under TXC, particularly at confining pressures above 20 MPa, the failure mode transitions to shear failure with prominent oblique shear cracks. Additionally, existing failure criteria are calibrated to match the strength envelop of UHPGC, with the Power-law failure criterion providing the closest fitting results. Subsequently, utilising both current and pre-existing TXC data, three commonly used concrete constitutive models, including HJC, K&C and CSC, are calibrated with respect to the dominant strength parameters for UHPGC in the finite element (FE) hydrocode ANSYS/LS-DYNA. Further, numerical simulations are conducted to evaluate the effectiveness of such three calibrated concrete models in replicating the response of UHPGC panels exposed to the contact explosion or projectile impact. The simulation results demonstrate that the K&C and CSC models effectively replicate the localised damage of UHPGC panels under contact explosions, while the HJC model more accurately simulates the depth of penetration (DOP) for thick UHPGC panels under projectile impact.