La0.67Ca0.33MnO3(001) thin films have been grown with pulsed laser deposition method, and the surface structures and electronic states have been characterized using scanning tunneling microscopy/spectroscopy (STM/STS). In the Mn-O terminated surface, insulating ( 2 × 2 )R45° reconstruction surface and metallic (1×1) reconstruction surface are observed. In the (La,Ca)-O terminated surface, the surface presents the stripe structure. The results obtained from the variable temperature STM/STS show that the ( 2 × 2 )R45° reconstructed surface persists in insulating phase in a temperature range of 144—300 K, which may shield the signal of possible insulator-metal transition occurred in bulk in STS measurements.