Adsorbates based on a number of P-block elements are known to accelerate Au deposition from sulfite as well as cyanide electrolytes. However, the nature of deposits from an electrolyte-additive system, and from the different electrolyte-additive systems, varies substantially. Optically smooth planar deposits coupled with superconformal filling of patterned features such as trenches and vias can be obtained from sulfite-Pb (and cyanide-Pb) electrolytes. With other additives superconformal feature filling is also observed, but it manifests with a geometry more akin to the extreme bottom-up filling seen during Cu filling of through silicon vias. Perhaps most interesting, deposits ranging from optically smooth surfaces to dense arrays of uniformly oriented nanowires can be obtained from sulfite-Tl electrolytes through adjustment of only the applied potential. I will discuss how electroanalytical measurements, coupled with mechanistic models, can help us understand, and in some cases predict, observed deposition behavior.