The applicability of locally dense basis sets (LDBS) to the accurate computational determination of gasphase bond dissociation enthalpies, substituent effects in para-substituted phenols, solvation energies, hydrogen-bond strengths, activation energies, and proton and electron affinities is examined. A general molecular partitioning scheme is presented and found to reproduce most properties to within 1 kcal/mol of the balanced basis set treatment. Slight modifications of the suggested partitioning scheme was required for the accurate determination of proton and electron affinities. Comparisons and implications of the locally dense basis set approach to current computational methods are presented. The present results suggest that the LDBS approach offers a computationally efficient alternative to large, balanced-basis set calculations of certain molecular properties and is a viable approach for large-molecule property computation.