Speaking to Italian daily La Repubblica, Antonio Vigni said: "Capitalia and Antonveneta are often linked with Monte Paschi without anything concrete...for various reasons they don't come into the ambit of our prospects.
"We are not obsessed by dimension: we will grow in Italy through sensible steps," he added.
Speculation had been rife that Montei Paschi would mount acquisitions amid a series of merger deals in the Italian market, coupled with an earlier announcement from Monte Paschi Chairman Giuseppe Mussari that the bank might be interested in Antonveneta.
Mr Vigni also used the interview to deny that Monte Paschi was among the consortium of Italian banks looking to take over telecommunications companies AT&T and America Movil.
News of Monte dei Paschi's intentions comes after it last month agreed to sell some of its life insurance business to French insurance provider Axa for $1.5 billion.