A positioning guide device with a guide wire in subclavicular venous access comprises a puncture needle. The puncture needle comprises a puncture needle cylinder, a needle head is arranged at the top end of the needle cylinder, a piston is arranged in the needle cylinder, a needle handle is arranged at the tail of the piston, a guide wire channel is continuously arranged in the needle handle and the piston, the guide wire is arranged in the guide wire channel, the top end of the guide wire penetrates through an inner cavity of the needle cylinder and a needle hole in the needle head, a magnet guide device is arranged on the outer side of the top end of the guide wire, and a gap is reserved between the magnet guide device and the top end of the guide wire. When the top end of the guide wire penetrates through the needle hole, the magnet guide device is placed in front of a sternoclavicular joint on a puncture side of a patient, a venous conduit faces a precava and is ensured to be positioned in the precava as the top end of the guide wire is under the action of magnetic force of the magnet guide device, the guide wire can be prevented from mistakenly entering abnormal portions such as an internal jugular vein, the success rate of subclavicular venepuncture can be increased, the pain of a patient is relieved, and the positioning guide device is safe, non-invasive, economical and environment-friendly.