For an energetic material with a definite composition, the substituent position is the most crucial factor to influence its physicochemical properties. Thus, it is becoming increasingly important to understand the impact of positional isomerism on multidimensional properties differences. Herein, we reported two new potential energetic melt-castable molecules, a pair of positional isomers (4-MMDNP and 5-MMDNP). These two explosives exhibit obviously different properties, including densities (Δρ = 0.03 g cm-3), melting point (ΔTm = 47.2 °C), decomposition temperature (ΔTd = 27.3 °C), stability (IS = 20 J, FS = 160 N vs IS = 10 J, FS = 40 N), etc., even though they share similar compositions and structures. Simultaneously, by analyzing crystal packing, intermolecular interactions, and monomolecular parameters, we were able to uncover the roots of property differences. Altogether, our results provide comprehensive molecular and crystal level insight into the effect of positional isomerism, which may be useful for new molecular design.