Emílio started playing professional soccer at the age of 16 in 1995, playing for XV de Piracicaba, a member of the state league of São Paulo. The next season he transferred to Rio Branco, another team in the state league of São Paulo. In 1997, Emílio signed with 1.

FC Köln of the German Bundesliga. He played for the youth team and finally worked his way up to the senior team, where he played several matches. In 1999, Emílio transferred to Alemannia Aachen, a team in the Second Division of the Bundesliga.


In 2001, Luciano Emílio made a return to Brazil to play for União Barbarense. After a brief stint at União Barbarense, Emílio made a move to the Honduran league to play for Real España in Honduras. He quickly established himself as a key player and won the league scoring titles in 2003 and 2004. He helped lead Real España to the Apertura Championship in 2003. In 2004, Emílio made a move to another Honduran team, Olimpia. Emílio won another scoring title in the Apertura in 2004 with Olimpia.


Emílio enjoyed a brief stint in Mexico in 2005 when he signed to the Mexican second division side Querétaro. He helped the team win the 2005 Clausura title, scoring 10 goals in the process. After playing for a short time with Querataro, Emílio made a return to CD Olimpia in 2005. He came in time to lead them to championships in the 2005 Apertura and the 2006 Clausura, during which he once again won the scoring title. In 2006, Emílio’s eight goals in the UNCAF Tournament were enough to propel his team to the 2007 CONCACAF Champions’ Cup. Ironically enough, Emílio would go on to play against CD Olimpia in the 2007 CONCACAF Champions’ Cup with his new club, D.C. United.


He signed with D.C. United on January 16, 2007, as a Senior International player, after completing his second stint with Honduran club Olimpia. Emílio debuted for D.C. United in the 2007 CONCACAF Champions’ Cup against Olimpia. He scored once in Tegucigalpa and twice in the return leg in Washington D.C., helping D.C United win 7–3 in aggregate.

He went on to score a fourth time in three games versus C.D. Guadalajara in the opening game of the CONCACAF semi-final. At the end of his first season with D.C. United, his team received the 2007 MLS Supporters’ Shield, the award for gaining the most points overall in a season. In the 2007 MLS season, Emílio had 20 goals and won the MLS Golden Boot award. Emílio won the 2007 MLS MVP award on November 14, 2007, and the inaugural MLS Newcomer of the Year Award on November 17, 2007.


After recovering from a lean start to the 2008 season, Emílio scored his first career MLS hat-trick on June 14 against New York Red Bulls. Though not originally signed under the Designated Player Rule, he later received a pay rise taking him over the maximum salary covered by the league, becoming a designated player. Emílio received a green card in August 2009 for permanent residency in the United States and counted no longer against DC United’s foreign player limit. Emílio rejected a new contract with D.C. United that would have seen him sign at a significantly lower salary. He later joined former club Rio Branco, but on April 28, 2010, Emilio signed a three-month contract to return to former club D.C. United. He later was released by D.C. United at the end of this short-term contract.


In August 2010 he joined Uruguayan club Danubio, which plays in Primera División Uruguaya. Luciano Emílio returned to Mexico to play for Atlante UTN in “La División de Ascenso” Mexico’s Second Division for the Clausura 2011 Tournament.