The scalable of ligated subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic, and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth, and postreduction etching are still not well understood. Herein, we demonstrate a prototype temperature-controlled flow reactor for qualitatively studying cluster formation in solution at steady-state conditions. Employing this technique, methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand, and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with a known length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates, and products synthesized in real time was characterized qualitatively using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold dusters was observed as well as smaller singly charged organometallic complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged organometallic complexes while reducing the abundance of triply charged species. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of batch reduction synthesis in solution.