The left-handed opener followed up his 112 for the Prime Minister's XI against the tourists in Canberra on Friday with another accomplished display as England's bowlers went largely unrewarded against the NSW batting on a flat SCG pitch.
At tea on the opening day, NSW were 218 for three off 56 overs, with Test aspirant Michael Clarke not out on nine and Aaron O'Brien on two.
Jaques was finally out when he hit to Steve Harmison at wide mid-off, off finger-spinner Ashley Giles, for 107 off 157 balls with 11 boundaries and two sixes off James Anderson and Monty Panesar.
Jaques continues to pressure incumbent Test opening pair Justin Langer and Matthew Hayden ahead of the November 23 first Ashes Test at Brisbane's Gabba ground.
Jaques put on 155 runs for the second wicket with Katich in as many minutes.
It was a dispiriting opening two sessions of play for the England tourists, with few chances and the NSW batsmen chugging along at more than four runs an over.
Test spearhead Harmison got the initial breakthrough when he bowled Ed Cowan for 26, with NSW at 38 for one, in his fifth over.
Katich, who had a life on 14 when Marcus Trescothick put down a straightforward chance at first slip off Andrew Flintoff, was out to a splendid outfield catch by Kevin Pietersen.
Katich, on 68, whacked Giles to deep mid-wicket where Pietersen took a tumbling catch just a metre inside the boundary rope. Katich batted for 194 minutes with six fours.
At tea, Harmison had taken 1-60 with new-ball partner Matthew Hoggard 0-40.
Skipper Andrew Flintoff had more encouragement after ankle surgery last July to get through 10 overs in the game without problems for 0-35.
Paceman James Anderson was belted by the NSW batsmen with 43 runs coming off his 11 overs, while Panesar had 0-22 off nine overs and Giles 2-17 off seven overs.
England left Chris Read out of their 14-man squad, giving an indication that Geraint Jones has the inside running on the wicketkeeping position for the Ashes opener.
Read was behind the stumps for England in the recent Champions' Trophy tournament in India, after being recalled to the Test side for the last two home Tests against Pakistan in August.
England and NSW have agreed to play 14 players during the three-day match -- which will not have first-class status -- but only 11 players a side can bat.
NSW 218 for 3 (Phil Jaques 107, Simon Katich 68, E Cowen 26; Giles 2 for 17, Harmison 1 for 60) Vs England