Until recently, organic vapor sensors using liquid crystals (LCs) have employed rigid glass substrates for confining the LC, and bulky equipment for vapor detection. Previously, we demonstrated that coaxially electrospinning nematic LC within the core of polymer fibers provides an alternative and improved form factor for confinement. This enables ppm level sensitivity to harmful industrial organics, such as toluene, while giving the flexibility of textile-like sheets (imparted by polymer encapsulation). Moreover, toluene vapor responses of the LC-core fiber mats were visible macroscopically with the naked eye depending on the morphology of the fibers produced, and whether they were oriented in specific geometries (aligned, or random). We identified two types of responses: one corresponds to the LC transition from nematic to isotropic, and the other we suggest is due to an anchoring change at the LC-polymer interface that influences the alignment. While we need to study the presence that defects can have in more detail, we noted that fiber mat thickness is crucial in attempting to understand how and why we are able to visualize two responses in aligned LC-fiber mats. Ultimately, we noted that the response of the polymer sheath itself (softening) to organic vapor exposure affects the liquid crystal confinement in the core. From the microscopic point of view, this will influence the threshold concentration that fibers in a mat will overall respond to. In this paper we will discuss three findings the morphologies enabling LC-core fiber mat response to vapor seen both micro- and macroscopically, how thickness of the fiber mat can play a role in the visualization of the responses, and the effect that the polymer structure has in the mat’s sensitivity threshold.