The invention provides a GaInP / GaAs / InGaNAs / Ge four-junction solar cell, comprising a Si support substrate, wherein a first contact layer of Ge or GaInAs, a Ge sub cell, a first tunnel junction, an InGaNAs sub cell, a second tunnel junction, a GaAs sub cell, a third tunnel junction, a GaInP sub cell and a second contact layer of InGaNAs or GaAs are arranged on the surface of the Si support substrate in sequence. The invention also provides a preparation method of the GaInP / GaAs / InGaNAs / Ge four-junction solar cell. The preparation method comprises the following steps: 1, a GaAs substrate is provided; 2, the second contact layer, the GaInP sub cell, the third tunnel junction, the GaAs sub cell, the second tunnel junction, the InGaNAs sub cell, the first tunnel junction, the Ge sub cell and the first contact layer are grown on the surface of the GaAs substrate in sequence; 3, the Si support substrate is provided; 4, the Si support substrate is bonded to the surface of the first contact layer; and 5, the GaAs substrate is stripped from the second contact layer, so that the GaAs substrate is removed.