Pisoni made a shift into politics at the 2006 state election, after incumbent Unley member Mark Brindal sought preselection for the electoral district of Adelaide.

Pisoni then faced Unley mayor and Labor candidate Michael Keenan in the election, and ultimately won the seat in a close result.

In January 2007, Pisoni was appointed Shadow Parliamentary Secretary for Multicultural Affairs, Transport, Infrastructure and Energy.

The margin was reduced to 8.9% after the district of Unley's electoral boundary was moved further west of Goodwood Rd to the Belair rail corridor.

[7] Pisoni was sworn in as the minister for Industry and Skills (DIS), a machinery of government change In response to the Joyce Review into key economic departments of the South Australian Government, saw industry policy shift to minister David Ridgway and the department of Trade Tourist and Investment (DTTI).