The molybdenum disulfide‐praseodymium sulfide (MoS2‐PrS) heterojunctions are optimally synthesized through a sophisticated three‐step procedure. Initially, MoS2 rods are synthesized using the micellar route followed by a solid‐state reaction, forming well‐defined structures. Subsequently, PrS nanoparticles are synthesized using the same method. In the final stage, PrS nanoparticles are evenly self‐assembled onto the MoS2 rods to create MoS2‐PrS heterojunctions. This is accomplished using a combination of polyethylene glycol and ethanol as a cohesive substance, assisted by the spin coating process. The MoS2‐PrS heterostructure has exceptional field emission characteristics, with a much lower turn‐on field of 2.6 V µm−1. This is in sharp contrast to the turn‐on fields of 3.5 and 4.3 V µm−1 reported in pure MoS2 and PrS, respectively. The emission current demonstrates remarkable stability at a predetermined value of 6 V µm−1 across 8 h, with variations limited to within ±2% of the mean value. The improved field emission (FE) capability of the MoS2‐PrS heterostructure is attributed to its high enhancement factor (β) of 2.1 × 103. The results highlight the capability of the MoS2‐PrS heterostructure emitter as a promising electron source in vacuum nano/microelectronic systems. Density functional theory calculation on electronic structure is performed to support the experimental results.