This study explored the differentiated neural correlates of mental rotation (MR) in preschoolers with high and low working memory capacity using functional near-infrared spectroscopy (fNIRS). Altogether 38 Chinese preschoolers (M = 5.0 years, SD = 0.69 years) completed the Working Memory Capacity (WMC) test, the Mental Rotation (MR), and its Control tasks (without MR). They were divided into High-WMC (N1 = 9) and Low-WMC (N2 = 18) groups based on the WMC scores. The behavioral and fNIRS results indicated that: (1) there were no significant differences in MR task performance between the High-WMC (Mmr = 23.44, SD = 0.88) and Low-WMC group (Mmr = 23.67, SD = 0.59); (2) the Low-WMC group activated BA6, BA8, BA 9, and BA 44, whereas the High-WMC group activated BA8, BA10 and BA 44 during mental rotation; (3) significant differences were found in the activation of BA44 and BA9 between the High-WMC and Low-WMC groups during mental rotation; and (4) the High-WMC and Low-WMC groups differed significantly in the activation of BA 9 and BA10 during the control tasks, indicating that both areas might be responsible for the group differences in working memory.