Calaiò started his football career at Torino making his league debut against Reggina on 6 January 2000, he scored a goal for Torino three minutes into his debut. He made 20 league appearances in total for Torino.
In January 2002 Calaiò was exchanged with Alessandro Cibocchi of Ternana with inflated price tag to create paper profit on both clubs (which Ternana was fined in 2010, 8 years later) and then a short spell with Messina followed. In January 2003, was loaned by Pescara and turned permanently in June 2004. He also returned to Torino Calcio in 2003 in exchange with Cibocchi again.
With Pescara, Calaiò solidified himself as an impressive striker, the club won promotion back into Serie B in 2003, with Calaiò scoring 20 times in his second season. In the third at Serie B, he scored 6 in the first half of the season.
In January 2005, Napoli Soccer at Serie C1 signed him for €2.85 million, he scored just 6 in the first season, but in the second he scored 18, won the champion and promotion back to Serie B with club. He scored 14 in his third season with Napoli, won promotion back to Serie A. With the arrival of Marcelo Zalayeta and Ezequiel Lavezzi, he had limited chances to play.
In July 2008, he joined fellow Serie A team, Siena in a co-ownership bid, for €2.3 million. in June 2009 Siena signed him outright for €1.25 million (which made Napoli register a financial loss of €1.05 million). He followed Siena relegated to Serie B in 2010 and finished as the runner-up and promoted back to top division. On 10 June 2011 he signed a new 3-year contract. Calaiò was one of the two starting strikers along with Mattia Destro in 2011–12 Serie A season, scoring 11 goals in 25 league matches until he broken his leg in March 2012.
On 11 January 2013, his transfer to former team Napoli was officially announced. He arrived on-loan with the option to make the switch permanent if Napoli qualified for the Champions League during the 2013 season.
On 11 July 2014, his transfer to Catania was officially announced. He signed a two-year contract with an option for a third.
On 3 August 2015 Calaiò was signed by Spezia.
On 4 August 2016 Calaiò was sold to Lega Pro newcomer Parma.
Calaiò capped for both Italy U21 and Serie B U21 selection which played the latter for the match 3–2 won Belgium U21 on 30 March 2004. He also received the Serie B U21 call-up for the match against Legnano.
He also call-up to 2000 UEFA European Under-18 Football Championship qualification and played in qualifying match in 2001 edition. Calaiò capped once for U17 team, at that time the feeder team of U18. (now called Italy national under-18 football team)
Calaiò is married to Federica, sister of Nicola Mora's wife. Both players played for Torino during the 2000–01 season and Napoli in 2004–05.2000–01 Serie B (Torino)
2005–06 Serie C1 (Napoli)
2006–07 Serie B (Napoli)
As of 12 September 2009
1Include 2 matches at promotion playoffs
2Include 3 matches at promotion playoffs