Rai bagged the white metal in men's 50-metre pistol event at the at the CEAR Juan Carlos I shooting range.
The 25-year-old Army marksman narrowly missed out on the gold medal to South Korean double Olympic champion and world record holder, Jin Jingoh, in a closely contested final. Jin shot a total of 192.3 over 20 shots in the finals while Jitu finished with a score of 191.1.
Jitu, currently ranked fifth in the ISSF world rankings, is having a dream year after having won the Commonwealth Games gold medal at Glasgow in July-August earlier this year. This is his fifth consecutive international medal in 2014.
He had won two back-to-back medals in the World Cup early this year, but this is undoubtedly the biggest feat he has achieved in his career so far.
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Expressing satisfaction over Rai's performance, Raninder Singh, president of the National Rifle Association of India (NRAI), said, "It's an extremely proud moment for us to see Jitu Rai become the first Indian athlete in all Olympic events to qualify for the Rio Olympics.
Ayonika Paul stormed into the final of the women's 10m air rifle event. Ayonika, the Commonwealth Games Silver medallist, shot a score of 620.8 to qualify in first place for the final.
There are six Olympic Quota places on offer in the women's air rifle in the World Championships.
Commonwealth Games silver medallist Gurpal Singh, however, shot 550/600 to finish 33rd while Om Prakash shot 548/600 to finish in 38th place in the men's 50m pistol event.