There is little love lost between Smith and Pietersen, who turned his back on his native South Africa to pursue a Test career with England.
And with six quicks in their squad - Dale Steyn, Makhaya Ntini, Morne Morkel, Monde Zondeki, Andre Nel and Jacques Kallis - South Africa have plenty of firepower at their disposal to give England's star batsman a tough workout.
"If we can be disciplined with our bowling like we have been in recent times and put the England batsmen under pressure we might then see if they have a soft spot," Smith wrote in his diary for the Bigstarcricket.com website.
"Kevin Pietersen is a key batter for England and I believe it's important we expose him early so bowling at their top order, numbers one to three, is going to be vital. If we can break through their top order early it will allow us to attack KP. I'm sure there will be some interesting battles."
Opening batsman Smith added England faced a difficult decision over how to be to re-integrate star all-rounder Andrew Flintoff, yet to regain full fitness following a side injury, into their Test team.
"Freddie Flintoff will give them some selection dilemmas like whether he is fit enough and then if he is do they play four bowlers or five and bat him at six. I'm very interested to see which way they go as it could prove a vital decision. My guess is that Michael Vaughan will want five bowlers."
South Africa arrive in England later this week with their opening tour match against Somerset on Sunday.
However, Smith does not expect to be playing in that match after injuring his hamstring while playing in the semi-finals of the Indian Premier League for eventual winners Rajasthan Royals.
But the left-hander said he was confident of being fit for the final warm-up match against Middlesex before the first Test of a four-match series at Lord's on July 10.
"I'm pleased to say that my fitness is getting there after my hamstring injury," Smith added. "I started running two or three days ago, which is a big stride to have made.
"There is still a lot of work to be put into the legs but I'm pretty happy with where I am - I'm quite positive. I am still on course for the Middlesex match on July 4 - our final game before the Lord's Test.
"It's not ideal to be recovering from an injury so close to such a big series but to be honest I needed a rest as I have played a lot of cricket this year and it has given me time to just take a break (from cricket) and spend some time in the gym again building up my fitness.
"We have a lot of cricket coming up as well so maybe it will work out for the best and give me the breather I needed."