Olympic bronze-medallist lost 3-4 to England's Anthony Ogogo amid warnings from the referee. In the final round of the bout, the Indian was warned twice - once for hitting his opponent on the back of his head and the second time for holding Ogogo.
Vijender's loss came as a massive shock to India. The host country even filed its protests against the harsh refereeing. But the jury, which reviewed the match, backed Canadian referee Michael Summers.
However, all was not lost as the host country's hopes for boxing medals were held up by Suranjoy Singh (52kg), Manoj Kumar (60kg) and Paramajeet Samota (+91kg).
All three pugilists have entered the finals assuring India of at least three silver medals in the boxing arena.
Suranjoy Singh beat Pakistan's Haroon Iqbal, Manoj Kumar defeated Bahamas' Valentino Knowles, and Paramajeet Samota overpowered Tonga's F A Junior in their semifinal bouts.