The preparation of gold nanomolecules with sizes other than Au(25)(SR)(18), Au(38)(SR)(24), Au(102)(SR)(44), and Au(144)(SR)(60) has been hampered by stability issues and low yields. Here we report a procedure to prepare Au(67)(SR)(35), for either R = -SCH(2)CH(2)Ph or -SC(6)H(13), allowing high-yield isolation (34%, ~10-mg quantities) of the title compound. Product high purity is assessed at each synthesis stage by rapid MALDI-TOF mass-spectrometry (MS), and high-resolution electrospray-ionization MS confirms the Au(67)(SR)(35) composition. Electronic properties were explored using optical absorption spectroscopy (UV-visible-NIR regions) and electrochemistry (0.74 V spacing in differential-pulsed-voltammetry), modes of ligand binding were studied by NMR spectroscopy ((13)C and (1)H), and structural characteristics of the metal atom core were determined by powder X-ray measurements. Models featuring a Au(17) truncated-decahedral inner core encapsulated by the 30 anchoring atoms of 15 staple-motif units have been investigated with first-principles electronic structure calculations. This resulted in identification of a structure consistent with the experiments, particularly, the opening of a large gap (~0.75 eV) in the (2-) charge-state of the nanomolecule. The electronic structure is analyzed within the framework of a superatom shell model. Structurally, the Au(67)(SR)(35) nanomolecule is the smallest to adopt the complete truncated-decahedral motif for its core with a surface structure bearing greater similarity to the larger nanoparticles. Its electronic HOMO-LUMO gap (~0.75 eV) is nearly double that of the larger Au(102) compound and it is much smaller than that of the Au(38) one. The intermediary status of the Au(67)(SR)(35) nanomolecule is also reflected in both its optical and electrochemical characteristics.