Liquid crystal (LC)/polymer composites are widely used for various applications such as polymer-dispersed liquid crystals, reflective displays, liquid lens, etc. These LC/polymer composites can be fabricated via encapsulation, polymerization-induced phase separation (PIPS), thermally-induced phase separation (TIPS), and solvent-induced phase separation (SIPS). Recently, multilayered coextrusion has been widely used for various applications ranging from mechanical enhancement to bioapplications. To utilize this flexible processing platform for liquid crystal applications, thermal stability and polymer miscibility of small molecules LCs at an elevated processing temperature are required. In addition to these two requirements, the extruded LC/polymer composites must exhibit phase separation upon cooling to realize the desired LC properties. In this investigation, a series of liquid crystals based on the 4,4’-alkyl substituted biphenyl moiety was synthesized and probed for their thermal stability, LC behavior, miscibility with a polymer matrix, and self-assembly upon cooling.