Vicente del Bosque's side proved far more clinical than their South American hosts and came out on top thanks to first-half strikes from the Barca pair and the Real Madrid man
David Villa opened the scoring with a free-kick after just five minutes and Pedro’s deflected effort made it two a quarter of an hour later as Spain converted their early chances.
Xabi Alonso then made it three with a free-kick of his own just before the interval to cap a useful few days for the Spanish after they had beaten USA 4-0 in a friendly in Foxborough on Saturday night.
Coach Vicente del Bosque made six changes from that match, bringing in Victor Valdes in goal, Andoni Iraola and Carlos Marchena at the back, Andres Iniesta in midfield and Pedro and Fernando Llorente in attack.
But it was David Villa who set the World Champions on their way after just five minutes, when he curled a right-footed free-kick past Venezuela keeper Renny Vega, who should have made the save.
Venezuela were having their moments at the other end and Giancarlo Maldonado came close for the hosts. The striker, who had a spell at Xerez last season, was denied by Valdes with only the Barca keeper to beat.
There was little in it at this stage, but the difference was crucial; Spain were taking their chances. And Pedro made it 2-0 after 20 minutes when he slotted a low, deflected shot into the corner from an angle.
Maldonado volleyed wastefully over from another great position moments later and Vega almost made a meal of Villa’s stinging drive at the other end, gratefully watching as his fumbled parry went over the bar instead of looping into the back of the net.
He was beaten again just before half-time, though, as Xabi Alonso curled a brilliant free-kick into the bottom corner. The Real Madrid midfielder did not take a single set-piece shot at his club this season, but may be doing so more often on this evidence.
Manu del Moral came on to make his debut after the break, while Santi Cazorla and David Silva were also introduced.
But Venezuela almost pulled a goal back straight away, when Alejandro Moreno poked wide within moments of the restart.
Another late substitute, Fernando Torres, then blasted over with only Vega to beat, while Valdes made a stunning save to keep out a fierce Tomas Rincon effort at the other end.
Venezuela kept pushing until the end, but the hosts were unable to find a way through and Spain cruised home to a second comprehensive victory in the space of a week.
Their next match is a mouthwatering friendly at San Siro against Italy in August.