The invention discloses a construction method of a photoelectric curtain wall of a glass film, which comprises mounting a support, laying a roof, mounting a cable tray, laying wires and cables, mounting a direct-current combiner box, wiring, mounting a low-voltage power distribution cabinet, wiring, mounting an inverter, mounting a grounding unit, mounting a monitoring system, mounting an adverse current prevention unit, and mounting a lightning protection facility. The invention combines the common conventional curtain wall (roof) with the photoelectric effect, makes the wall surface or roof have exterior protection functions, has rain-escaping, shading, wind proofing, sunstroke preventing and winter protection functions, simultaneously utilizes solar energy to generate power, and has obvious economic benefits.