Four esteryl-bridged energetic compounds have been derived from 2,2,2-trinitroethanol with polynitro benzoic acids and characterized via IR, multinuclear NMR spectroscopy, elemental analysis and differential scanning calorimetry (DSC). The structures of 2,2,2-trinitroethyl-2,4,6-trinitrobenzoate (5), bis(2,2,2-trinitroethyl)-4,6-dinitroisophthalate (6), bis(2,2,2-trinitroethyl)-2,5-dinitroterephthalate (7) and bis(2,2,2-trinitroethyl)-2,4,6-trinitroisophthalate (8) were further confirmed by X-ray diffraction studies, which show favorable densities (1.804–1.850 g cm⁻³). Interestingly, most of the polynitro esters decompose at temperatures over 180 °C (except for 6: 171.6 °C), which thus exhibit good thermal stability. In addition, performance calculations give detonation pressures and velocities for the ester derivatives in the range of 30.4–32.9 GPa and 8267–8559 m s⁻¹, respectively. The esteryl-bridged compounds possess acceptable impact sensitivities (14–22 J), friction sensitivities (240–360 N), and electrostatic sensitivities (0.20–0.32 J). These values indicate that polynitro esters can be candidates as promising energetic materials.