The composite of linear low density polyethylene (LLDPE) with carbon black (CB) and inorganic flame retardant (aluminum hydroxide, Al(OH)3) was prepared by melt-blending method. The effect of cross-linking on the stability of positive temperature coefficient (PTC) of composite and the elimination of negative temperature coefficient (NTC) of composite were investigated. LLDPE was chemically cross-linking with different contents of initiator (dicumyl peroxide, DCP). The cross-linking effects of composite were analyzed by gel content analysis, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). By the effect of DCP, not only the composite appeared a high PTC intensity, but also the NTC effect of composite was eliminated. In this investigation, the optimum PTC intensity of composite reached 5.87 orders of magnitude for the composition of LLD0.l0C33.7A28, and the PTC transitional temperature of composite decreased with increasing of DCP content. In addition, the good reproducibility of composites was proved by thermal cycling, and successfully passed the test of over-voltage resistance.