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He coached Sevilla FC between 1960 and 1963. In the 1961/62 season he led the team to sixth place and managed to reach the final of the Spanish Cup, which they lost 2-1 to Real Madrid. The presence in the final meant qualification to play in the European Cup Winners' Cup the following season. The decline in the team's form in the 1962/63 season forced him to be replaced by the legendary José María Busto.
After Sevilla FC played in the relegation play-offs in 66/67, Antonio Barrios returned to the club for the 1967/1968 season with the aim of getting the team back on track and halting the downward trend of recent years. After only 3 wins in 18 league games, he had to be replaced by Juan Arza, who failed to avoid relegation after 31 consecutive years in the first division.
He coached Sevilla FC in the 1959/60 and 1960/61 seasons. Among his achievements was that the team played attractive and effective football. Under his guidance, the team had one of the best seasons after Helenio Herrera's departure, finishing fourth, and beating some of the strongest teams in the country. In his second season the team finished in mid-table.
The Biscay-born coach replaced Janos Kalmar until the end of the 1958/59 season, leaving the team out of danger in twelfth place.
He managed the team for only ten matches in the 1958/59 season. Only one win in ten matches cost him his job. He was accompanied by Mario Klug as translator, who shortly afterwards took over the reins of sides in the youth ranks.
He coached the team for only half a season in 1957/58, going down in history as the coach who led the team in its first continental matches. He was sacked in December 1957 due to poor results.