In this work, two novel routes to synthesis cross-linked polypropylene (PP) are introduced by using two different precursors (2-thiophenemethyl amine (TMA) and 1-(3 aminopropyl) imidazole (API)), both cross-linked with 1,1′-(methylenedi-4,1-phenylene) bismaleimide (BM) at two different annealing temperature values (T = 50 °C and T = 150 °C). Both Diels–Alder (DA) and Michael addition reactions were successfully performed with TMA and API, respectively, albeit with different reactivity. Imidazole clearly shows a higher reactivity compared to thiophene. In addition, an increase in annealing temperature leads to a higher degree of cross-linking. The highest degree of cross-linking was obtained by the imidazole product after annealing at 150 °C (IMG1A150) as evident from the highest complex viscosity (|η*|) value of IMG1A150. A difference in rheology and thermal properties between the imidazole and thiophene cross-linked products was also observed. However, both products have superior melt properties and thermal stability compared with the starting material. They show processability at high temperatures. The melt flow behavior and de-cross-linking at higher temperatures can be tuned depending on the choice of imidazole or thiophene. This study shows an advance on the cross-linked PP processing and its product performances for further application on the commercial scale.