We synthesized three novel diglycidylester-terminated liquid crystalline epoxy (LCE) resins containing various liquid crystalline backbones to investigate the thermal conductivity of composites filled with alumina (Al2O3) particles and the results are compared to that of the composite with diglycidylether-terminated LCE resin which differs only in the structure of terminal epoxy linkage. The results showed that LCE resins displayed distinct nematic liquid crystalline phases at wide temperature ranges and all cured systems exhibited well-reserved nematic phases. The thermal conductivity of novel diglycidylester-terminated LCE resin containing composite is higher than that of diglycidylether-terminated LCE resin containing composite.