The invention belongs to the field of photovoltaic devices, and particularly discloses a multi-junction GaAs laminated laser photovoltaic cell, which comprises a substrate, at least two GaAs sub-cells and tunneling junctions located between two adjacent GaAs sub-cells, wherein the at least two GaAs sub-cells are sequentially laminated on the substrate. According to the multi-junction GaAs laminated laser photovoltaic cell, multiple GaAs sub-cells are connected in series by using the tunneling junctions, an isolation groove does not need to be etched, and the effective sunlight area of the multi-junction GaAs laminated laser photovoltaic cell is increased by series connection in a lead manner, thereby obtaining relatively high output voltage. Meanwhile, an etching process and a filling process are avoided. A conductive substrate is adopted by the multi-junction GaAs laminated laser photovoltaic cell, so that heat dissipation can be effectively improved and the working temperature is reduced. The invention further discloses the photovoltaic device with the multi-junction GaAs laminated laser photovoltaic cell and the preparation method of the photovoltaic device. According to the photovoltaic device, the series resistance of the photovoltaic device can be reduced and the filling factor can be improved.