Powder metallurgy (PM) steels containing boron form an attractive group of alloys because of the important densification that can be achieved through permanent liquid phase sintering (LPS). However, upon solidification, such liquid phase is known to form borides or borocarbides. Recent works have shown that some alloying elements have significant interactions with the LPS of PM steels containing boron. More specifically, it is suspected that the concentration of prealloyed molybdenum influences the formation of boride/borocarbide upon cooling at the end of the sintering cycle. Therefore, the main objective of this work is to describe the relationship that exists between the concentration of prealloyed molybdenum and the crystal structure of the boride/borocarbide eutectic component that typically forms in PM steels containing boron. A master alloy made of iron-manganese-nickel-boron-carbon was utilized to introduce boron, thus providing enhanced sintering through LPS. Characterization in optical and scanning electron microscopy combined with electron-backscattered diffraction and energy-dispersive X-ray spectrometry (EDS) revealed that increasing the prealloyed molybdenum content not only increased the volume fraction of liquid phase but also modified the morphology and the nature of the boron-rich eutectic. Changing the prealloyed molybdenum content from 0.5 to 0.85 wt.% transformed the discontinuous M2B boride to a continuous M23(C,B)6 borocarbide phase, causing a drastic decrease in strength despite the higher densification observed at 0.85 wt.% molybdenum. The effect of molybdenum on the LPS process of boron PM steels is undeniable and was found to occur after the initial formation of the liquid phase. Indeed, differential scanning calorimetry revealed no difference in the endothermic melting peaks temperature for both concentration of molybdenum.