The Brazilian, who last led away a race in his home country in 2008, finished final practice at Barcelona's Circuit de Catalunya with the quickest lap of the weekend so far.
Massa posted a time in his Ferrari of one minute 21.901secs, just 0.006secs ahead of Lotus' Kimi Raikkonen who is bidding to become the first driver to win at this circuit with three different teams.
Red Bull's Mark Webber, winner of this race in 2010, was third on a highly competitive timesheet as the top 11 drivers were separated by under a second.
The veteran Australian was followed by Romain Grosjean in his Lotus, with the Frenchman back in form after his third place in Bahrain three weeks ago.
Red Bull's three-times champion Sebastian Vettel and Fernando Alonso in his Ferrari, who were first and second yesterday and separated by 0.017secs, were fifth and sixth at the end of hour-long run.
The title contenders were split by 0.027secs on this occasion, albeit over three tenths of a second behind Massa.
With Red Bull, Ferrari and Lotus occupying the top six places, there was no room for Mercedes in the hierarchy as Lewis Hamilton and Nico Rosberg were down in ninth and 11th.
The duo have been on pole at the last two races, but this time around Mercedes appear to be struggling.
Hamilton had Force India duo Paul Di Resta and Adrian Sutil ahead of him in the pecking order, whilst Toro Rosso's Jean-Eric Vergne also managed to get ahead of Rosberg, who finished 0.938secs adrift of Massa.
As for McLaren, there was a small improvement, at least in time if not in position as Jenson Button was again 12th, 1.250secs off the pace.
Despite two new front wings arriving overnight in a bid to close the gap on their rivals given the lack of performance from the upgrades on the car this weekend, neither were used, and are unlikely to be for qualifying, a McLaren spokesman confirmed.#Sergio Perez was down in 14th, almost 1.5secs down, with even fellow Mexican Esteban Gutierrez - who replaced him at Sauber for this year - ahead of him in 13th.
Towards the rear were the usual suspects in Williams, Marussia and Caterham, with British rookie Max Chilton 21st and 3.2secs adrift, with Giedo van der Garde slowest, a further 0.2secs down.