Caio said the recruitment process is already underway.
“[The new staff] are needed to modify and reinforce the professional profile of postal service workers in order to better serve the public,” he was quoted by TGCom24 as saying.
In an interview with The Financial Times on Sunday, Caio said the initial public offering (IPO) “is a very large privatization by Italian standards and opens up the privatization window after a long freeze”.
The government announced in July that it would list a 40 percent stake in Poste Italiane on the Milan stock exchange as part of a drive to privatize state-run assets.
It hopes to raise between €2.7 billion and €3.9 billion from the sale as part of premier Matteo Renzi's wider plan to raise €12 billion for the state's coffers.
Caio said the IPO “gives us the opportunity and the challenge to show what we are capable of as a company and a country.”
As an investor roadshow got underway on Monday, Caio said the IPO “will contribute to the modernization of the country”.
The fresh round of recruitment comes a year in to a controversial restructuring drive which has seen some of its 145,000 staff taking early retirement and 300 post office closures. A small group of employees gathered outside Milan's stock exchange on Monday to protest against the privatization, TGCom24 reported.
Poste Italiane, which is 153 years old, also has a thriving banking arm. The company holds around €240 billion in savings' deposits and has annual revenues of €24 billion.
The government has also proposed the partial sale of railway group Ferrovie dello Stato and national aviation group, Enav.