Cambridge responded with scores early in each half from James Richards and Niall Conlon, with Richards adding a conversion and penalty, before replacement flanker Joe Wheeler drove over on the hour to keep their hopes alive.
Then they struck with a sensational fourth try through wing James Wellwood with Richards converting to set up a nerve-tingling final four minutes when Oxford should have been home and hosed.
Ultimately the game had been taken away from them when Oxford skipper Peter Clarke galloped in for a fourth try just after the break, Tom Gregory adding two penalties and a conversion, even though they were forced to spend most of the second half on the defensive.
Oxford's attacking vigour would also have won warm nods of approval from former Dark Blue greats at the ground, with David Kirk (New Zealand), Rob Egerton (Australia) and David Evans (Wales) among the victorious 1988 Oxford side reunited 20 years on.
Cambridge were combative enough up front but had no answer to the fluidity of Oxford's backline Catling's initial strike in the sixth minute, when he fended off Wellwood and Richards down the left.
Richards responded with a try on the right after Jon Dawson's forwards - with Australia's Dan Vickerman packing down in the second row - laid siege to the line and the full back converted to nudge his side in front.
Richards and Gregory then traded penalties before Oriental Studies student Catling changed the complexion of the game by scoring twice in 10 minutes before the break.
He beat Wellwood and Richards again down the left, Gregory converting, before another break saw Richards sin-binned for blocking Catling as he chased a chip ahead.
The challenge was punished immediately as Catling came infield and took fly half Ross Swanson's reverse pass to score his third and send Oxford in 23-10 up.
Gregory's second successful penalty followed immediately after the interval before Cambridge found a way back into the game, driving prop Conlon over in the corner in the 46th minute.
But Oxford put their foot on the gas again, this time through their forwards with number eight Peter Wright bursting out of a maul and putting skipper Clarke in for a 20m run to the line.
Wheeler added fresh impetus in the Light Blues' back-row and stayed on his feet to force his way over 20 minutes from time, Richards adding the extra points.
Tries: Catling 3, Clarke.
Conversions: Gregory 2.
Penalties Gregory 3.
Tries: Richards, Conlon, Wheeler, Wellwood.
Conversions: Richards 3.
Penalty: Richards.
Yellow card: Richards 34-44.
Oxford: Chris Mahony (Keble); Sean Morris (Somerville), Jonathan Burnett (University), Tom Gregory (Kellogg), Tim Catling (Pembroke); Ross Swanson (New), Brendan McKerchar (Keble); Richard Lutton (Linacre), Anton Oliver (Worcester), Wayne Thompson (St Cross), Ian Kench (St Cross), Robert Payne (Worcester), Stan McKeen (Harris Manchester), Peter Clarke (St Cross, captain), Peter Wright (Mansfield).
Replacements: Dan Rosen (Worcester), William Johnson (Pembroke), Nick Van Zyl (Green/Templeton), Chris Davies (St Edmund Hall), Toby Henry (Linacre), Alex Cheesman (St Edmund Hall), William Browne (Balliol).
Cambridge: James Richards (Hughes Hall); James Wellwood (St Edmund's), Chris Lewis (St Catharine's), Mark Ranby (St Edmund's), James Greenwood (Hughes Hall); Alex Reid (St John's), Douglas Rowe (Hughes Hall); Niall Conlon (St Edmund's), Matt Crockett (St Edmund's), Jon Dawson (St Edmund's, captain), Matt Wilson (Selwyn), Dan Vickerman (Hughes Hall), William Jones (St Edmund's), Tom Malaney (St Edmund's), Trevor Boynton (Hughes Hall).
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