While inhomogeneous thin conductive films have been sought after for their flexibility, transparency, and strength, poor control in the processing of these materials has restricted their application. The versatile layer-by-layer assembly technique allows greater control over film deposition, but even this has been hampered by the traditional dip-coating method. Here, we employ a fully automated spin-spray layer-by-layer system (SSLbL) to rapidly produce high-quality, tunable multilayer films. With bilayer deposition cycle times as low as 13 s (~50% of previously reported) and thorough characterization of film conductance in the near percolation region, we show that SSLbL permits nanolevel control over film growth and efficient formation of a conducting network not available with other methods of multilayer deposition. The multitude of variables from spray time, to spin rate, to active drying available with SSLbL makes films generated by this technique inherently more tunable and expands the opportunity for optimization and application of composite multilayers. A comparison of several polymer-CNT systems deposited by both spin-spray and dip-coating exemplifies the potential of SSLbL assembly to allow for rapid screening of multilayer films. Ultrathin polymer-CNT multilayers assembled by SSLbL were also evaluated as lithium-ion battery electrodes, emphasizing the practical application of this technique.