Styrene-co-chloromethyl styrene copolymers chemically modified with various kinds of monoamines or diamines were synthesized. Their sensing properties based on toluene vapor sorption/desorption behaviors were measured using a quartz crystal microbalance (QCM) technique. Introduction of aliphatic diamine compounds having a proper chain length (e.g., N,N-dimethyl-1,3-propanediamine (DMPDA)) into the structure of the copolymer realized improvements to the toluene vapor sorption capacity, the response time, and reversibility compared to the conventional polymer coatings. FTIR analysis suggests the formation of a loosely cross-linked structure, resulting in the promotion of toluene vapor diffusion into the film.