The British Overseas Territory, which lies off the south coast of Spain, became the 54th nation to join European football's governing body in May.
There had been opposition from Spain but the Gibraltar FA won a case at the Court of Arbitration for Sport obliging UEFA to accept them as a member.
Their historic first match was staged at the Estadio de Algarve in neighbouring Portugal this evening and Allen Bula's men claimed a creditable goalless draw against a Slovakia side placed 65th in FIFA's world rankings.
That was a decent start to international life for Gibraltar, but it was not the most impressive result of Tuesday's international friendlies with South Africa claiming a shock 1-0 win over reigning world and European champions Spain at Johannesburg's Soccer City stadium.
A second-half goal by Bernard Parker earned South Africans a surprise triumph in the same stadium where La Roja won the 2010 World Cup.
The Kaiser Chiefs forward beat Victor Valdes after 57 minutes to stun Vicente del Bosque's side, who produced one of their poorest performances in recent memory to lose only their second match in more than three years.
In another match that revived memories of the last World Cup, Germany beat England 1-0 at Wembley thanks to a first-half Per Mertesacker header.
It was the first meeting between the two old rivals since Germany's 4-1 last-16 win in South Africa three years ago and condemned England to back-to-back home defeats for the first time in 36 years following Friday's loss to Chile.
Holland, the side Spain beat in the final to be crowned world champions, were held to a goalless draw by Colombia at the Amsterdam ArenA.
The Dutch had to play almost an hour with a man less following Jeremain Lens' red card but they still managed to stretch their unbeaten run to 17 games.
Belgium, a side widely tipped to do well in next year's World Cup, suffered their second successive friendly loss as they were beaten 3-2 by Japan having also been downed by the Colombians on Friday.
The Red Devils scored first and last through Kevin Mirallas and Toby Alderweireld but Japan struck three times in between through Yoichiro Kakitani, Keisuke Honda and Shinji Okazaki.
In other friendlies, Russia battled back from a goal down to beat South Korea 2-1, Turkey snatched a late 2-1 win over Belarus, while Austria saw off the USA courtesy of a first-half Marc Janko effort.
Scotland continued their good showing under Gordon Strachan with a 1-0 win over Norway, Scott Brown the match-winner, while the Republic of Ireland recorded a goalless draw against Poland.
Also, Slovenia beat Canada 1-0, Malta defeated Faroe Islands 3-2 and Estonia were 3-0 victors at Liechtenstein