Recent studies have shown that young children’s orientation sensitivity is correlated with their reading ability. However, the development of orientation sensitivity to Chinese characters with different complexities (e.g., simple characters and compound characters) in preschool children is unknown. To fill this gap, the current three-year longitudinal study aimed to investigate the development of orientation sensitivity to Chinese simple characters and compound characters. A total of 50 Chinese children were first tested at their first kindergarten years (T1: mean age = 3.62 years) and then tested annually on a variety of tasks for three years (T2: mean age = 4.63 years; T3: mean age = 5.58 years). Children’s orientation sensitivity to Chinese characters was assessed using two perceptual-matching tasks. The results showed that the inverted and mirrored orientation sensitivity to Chinese characters demonstrated different developmental trajectories. Specifically, children possessed inverted and mirrored orientation knowledge of Chinese simple characters at the age of 4. They also displayed sensitivity to inverted Chinese compound characters at the age of 5. However, mirrored orientation knowledge of Chinese compound characters did not emerge until the age of 5. These results suggest that children’s inverted orientation knowledge of Chinese characters developed earlier. Moreover, the complexity of Chinese characters affected the development of orientation knowledge of Chinese characters.