MXenes, 2D nanomaterials derived from ceramic MAX phases, have drawn considerable interest in a wide variety of fields including energy storage, catalysis, and sensing. There are many possible MXene compositions due to the chemical and structural diversity of parent MAX phases, which can bear different possible metal atoms “M”, number of layers, and carbon or nitrogen “X” constituents. Despite the potential variety in MXene types, the bulk of MXene research focuses upon the first MXene discovered, Ti₃C₂T. With the recent discovery of polymer/MXene multilayer assemblies as thin films and coatings, there is a need to broaden the accessible types of multilayers by including MXenes other than Ti₃C₂T_z; however, it is not clear how altering the MXene type influences the resulting multilayer growth and properties. Here, we report on the first use of MXenes other than Ti₃C₂T_z, specifically Ti₂CT_z and Nb₂CT_z, for the layer-by-layer (LbL) assembly of polycation/MXene multilayers. By comparing these MXenes, we evaluate both how changing M (Ti vs Nb) and “n” (Ti₃C₂T_zvs Ti₂CT_z) affect the growth and properties of the resulting multilayer. Specifically, the aqueous LbL assembly of each MXene with poly(diallyldimethylammonium) into films and coatings is examined. Further, we compare the oxidative stability, optoelectronic properties (refractive index, absorption coefficient, optical conductivity, and direct and indirect optical band gaps), and the radio frequency heating response of each multilayer. We observe that MXene multilayers with higher “n” are more electrically conductive and oxidatively stable. We also demonstrate that Nb₂CT_z containing films have lower optical band gaps and refractive indices at the cost of lower electrical conductivities as compared to their Ti₂CT_z counterparts. Our work demonstrates that the properties of MXene/polycation multilayers are highly dependent on the choice of constituent MXene and that the MXene type can be altered to suit specific applications.