We studied the effects of Mo substitution on the structural, transport, and magnetic properties of the La0.7Ca0.3Mn1−xMoxO3 (x ≤ 0.1) samples. Powder X-ray diffraction analysis reveals that the samples studied crystallize in the orthorhombic structure with space group Pbnm. Both particle size and morphology change significantly as the Mo content x varies. The metal-insulator transition temperature (TMI) and Curie temperature (TC) decrease monotonically as x increases. Magnetization data reveal that long-range FM ordering persists in all samples and the saturation moment decreases linearly as x increases. The smaller depression rate of dTC/dx observed is mainly ascribed to the increased amount of Mn2+ ions with Mo doping, which opens the FM coupling between Mn2+–O–Mn3+ in the samples.