The experimental energy of activation (E,) of the single-step concerted oxidation process of aliphatic primary alcohols by quinolinium bromochromate (QBC) are correlated with the theoretically evaluated global electrophilicity values (w) [as proposed by Parr et al. (J. Am. Chem. Soc. 1999, 121, 1922)]. Conceptual justification in favor of correlating w of the substrate with E-a involved in a single-step concerted reaction is also discussed. The evaluated w values at HF/cc-pVTZ and MP2/6-31G(d,p) methods are found to be as expected (when we consider structural aspects), although there are some inconsistencies in other methods [e.g., HF/6-31G(d,p), B3LYP/cc-pVTZ, BLYP/dnp, PW91/dnp, PWC/dnp, VWN/dnp]. The reasons for the inconsistencies, even with a superior B3LYP/cc-pVTZ method, are discussed thoroughly. It is observed that the higher the value of w, the more the value of E,, involved in the process of oxidation of primary alcohols by QBC. The present study also reveals that the apparent success of insignificant (i.e., much smaller) local electrophilicity values (s(OOH)(+)), evaluated using Hirshfeld population analysis (HPA), in explaining observed trend of experimental E-a values turns out to be ambiguous when more significant (i.e., much larger) local nucleophilicity values (s(OOH)(+)) are also compared. This is evident from I the corresponding correlation coefficient values.