The 31-year-old from Kirkcaldy was only one under at the turn, but started the back nine with four successive birdies and made another from 10 feet on the 358-yard 17th.
Canizares, whose father Jose Maria kept the Ryder Cup in European hands at The Belfry in 1989, also made a late run, collecting five of his seven birdies on the outward half after turning in 34.
They lead by a stroke from Italian Federico Colombo, but former Open champion John Daly - fourth in Qatar two weeks ago - finished the day second-last following a seven-over-par 79.
That contained two penalty drops away from the trees in a triple-bogey eight at the 14th and then a ball in the water en route to a closing bogey six.
Whiteford finished 63rd on last season's European Tour money list, with five top-10 finishes, including third place at the Alfred Dunhill Championship in South Africa.
He arrived in India after missed cuts in Qatar and Dubai, but made his only mistake on the 486-yard fifth, rated the toughest hole on the DLF course which last year saw local man SSP Chowrasia win with a 15-under total.
Canizares won the 2006 Russian Open in only his third Tour start as a professional and was twice involved in play-offs two seasons ago, losing first to Peter Hanson in Majorca and then to Miguel Angel Jimenez at the French Open.
Welshman Jamie Donaldson, seeking his first victory in the circuit in approaching 250 starts, is tied for fourth on four under with Indian Himmat Rai, French pair Gregory Havret and Jean-Baptiste Gonnet and Thai duo Thongchai Jaidee and Kiradech Aphibarnrat.
Whiteford told the European Tour's website: "It was the first time I've hit the fairways in months.
"I hit a lot more drivers than people usually do out there and just took advantage of the course and bullied it a little.
"It can bite you easily though if you're not careful. I had a bad one down the last, but apart from that it's mainly the driving that was loads better today."
Canizares said: "The only mistake I made was missing a short putt on the seventh. I had a couple of wayward drives, but nothing serious and I felt very comfortable.
"Hopefully I can keep this going and be in contention going into the final round."