The CuxSi1−x thin films have been successfully fabricated by pulsed laser deposition (PLD). The influences of laser energy fluency (I0) and deposition temperature (Td) on the phase structure were investigated. The results show that Cu deposited on Si (001) at I0 = 0.5-2.0 J/cm2, and η”-Cu3Si formed on Si (111) at I0 = 1.0-2.0 J/cm2. The films were consisted of Cu, η’-Cu3Si, ε-Cu15Si4 and δ-Cu0.83Si0.17 at Td = 100-500 °C on Si (001). The films were the single phase of η-Cu3Si at Td = 700 °C. In the case of Si (111), the phase structures transformed from Cu to Cu + η’-Cu3Si to η’-Cu3Si to η’-Cu3Si + η-Cu3Si with the increasing of Td. Rectangular grains were formed on Si (001), whereas triangular grains on Si (111). Cu (001) film was epitaxially grown on Si (001) at I0 = 1.5 J/cm2 and Td = 20 °C. η-Cu3Si (001) epitaxial layer was formed on Si (111) at I0 = 1.5 J/cm2 and Td = 700 °C. The epitaxial relationships of Cu (001)[100]//Si (001)[110] and η-Cu3Si (001)[-110]//Si (111)[11-2] were identified.