The layer-by-layer (LbL) assembly of carboxylated single-walled carbon nanotubes (SWCNT) is demonstrated to tune the electrochemical pH sensitivity of thin-film devices. The positively charged amine containing weak polyelectrolyte (wPE) is used as a counter species to control the proximal ions. The LbL assembly process is monitored by the quartz crystal microbalance, which results in the linear growth of a multilayer. The amount adsorbed is strongly dependent on the surface charge of previously deposited species. However, the thickness of the multilayer is determined by both the amount adsorbed and the coiling of polyelectrolyte chains. Indeed, electrical and structural characteristics of the (wPE/SWCNT) multilayer thin film are obtained according to the acid dissociation constants of amino groups in wPE. The electrochemical pH sensitivity in the physiological range demonstrates the effects of both charge carrier doping/trapping and proximal ions on the conductance of the SWCNT multilayer. Although doping/trapping shows the decreasing conductance, the proximal ion effect reveals the increasing conductance with pH in the basic region as a result of the p-type semiconducting nature of SWCNTs and the ability of wPE to capture hydrogen ions. This work sheds light on the applicability of nanostructured and/or engineered functional thin films of SWCNTs as chemical and biological sensors.