[12] De Luca was elected to the Salerno city council in 1990, holding the posts of both Commissioner of Public works and Deputy Mayor.

In the spring of 1993, he was promoted to the office of mayor of Salerno due to the resignation of Vincent Giordano, who found himself involved in the ongoing Tangentopoli investigation.

The subsequent elections marked a significant success of De Luca's Progressive List for Salerno, with 57.8% of votes in a second ballot against Giuseppe Acocella, of the centre-right coalition.

[14] On 31 May 2001, he was elected to the Chamber of Deputies with a percentage of 55.4% of the votes, the highest one obtained by a candidate of The Olive Tree coalition in Southern Italy.

In the 2008 Italian general election, he was unable to run due to the incompatibility provided by law between the offices of member of Parliament and mayor of a city with more than 15,000 inhabitants.

His centre-right coalition rival Stefano Caldoro, a former minister and leader of the New PSI (a party that merged into Silvio Berlusconi's The People of Freedom in 2009) won by a convincing margin, thanks to a 20% swing in favor of the centre-right coalition, which included the Union of the Centre led by Ciriaco De Mita, an influential former leader of Christian Democracy.

[22] Notably, Italian software house DigiLabSoftware satirized De Luca's statements with some HTML browser games freely playable on their website, which attracted some press attention.

[24] In November 2021, De Luca was investigated for corruption regarding a scandal involving the maintenance of city streets, public greenery and parks of Salerno.