From 145 for seven, India recovered to finish the day at 290 for nine as Rahane made 103 and put on 90 with Bhuvneshwar Kumar (36).
Rahane said: "I'm really happy with this special hundred at Lord's. I just looked and saw my name on the board, it's a proud moment. I have to give credit to the top order, they batted well in a tough situation. We had a great day. Tomorrow morning, maybe a quick 20 or 30 runs, it's another crucial day."
The wicket at HQ certainly had a lot more life in it than that seen in the first Test at Trent Bridge, but Rahane relished the chance to test himself. "Playing Test cricket outside your country is a challenge and I love challenges," he said. "I love playing on this kind of wicket."
Ben Stokes, the all-rounder, was frustrated after England again struggled to finish their opponents off having taken top-order wickets.
"We got ourselves in a brilliant position," said the Durham man. "The tail wagged a bit and credit to Rahane, he played a really good knock. You have to give some credit to Kumar as well, he seems to hang around. I thought we were unfortunate with the amount of play-and-misses and nicks through the slips."
James Anderson led the way with four for 55 on a surface offering pace and movement, with Stuart Broad taking two for 79 and a wicket apiece for Stokes, Liam Plunkett and Moeen Ali. "It's good to see the ball carrying through and swinging," said Stokes. "I don't think we're too far off."
Rahane's skilled resistance allowed India to defy the greenest of Lord's pitches, a total contrast to the dead wicket at Trent Bridge that staged last week's opening draw.
Anderson set aside his disciplinary worries to tick off a clutch of new statistical landmarks, but number five Rahane's second Test hundred ensured India were no compliant fall guys after being put in to deal first with awkward conditions.
Anderson will face a preliminary International Cricket Council hearing next Tuesday after India instigated a Level Three charge against him for his part in an altercation with Ravindra Jadeja during the first Test.
He was not necessarily at his best, but still finished with four wickets - including that of Rahane with a nonchalant one-handed return catch.
Rahane's 151-ball century was built on admirable defence but contained 15 fours too - and a memorable straight six from the crease off Anderson, with the second new ball.
Anderson and Broad erred in line on a sunny morning and wicketkeeper Matt Prior missed two catches as India largely kept the bowlers at bay. The hosts were much-improved in the afternoon, and reaped just rewards, before Rahane and Kumar - their stumbling block in the first Test, with two half-centuries - held them up for 24 overs.
Earlier, Gary Ballance held a neat catch at third slip when Anderson found the edge with movement down the slope to Shikhar Dhawan.
Broad might have reduced India to 11 for two had Prior managed to cling on to a tough chance diving low to his right in front of slip, with opener Murali Vijay on nought.
Anderson began with five maidens on a day when he would also become all-time leading wicket-taker at Lord's and in Tests between England and India, but he and Broad both allowed Vijay and Cheteshwar Pujara the freedom to leave a high percentage of deliveries and often watch the ball swing and seam harmlessly by.
Vijay fell to first-change Liam Plunkett with an edge to third slip, where Ballance was safe again with a very sharp chance, but Virat Kohli was dropped by Prior on 20 off the final ball of the session.
It was not a costly slip, Kohli giving Prior a second chance when he edged some outswing behind after Anderson switched to the nursery end.
Pujara's vigil extended to 117 balls before Stokes bowled him with an especially good delivery.