There's no nonstop path from the Sonoran Desert to the Mediterranean, which is precisely why routing strategy matters more on this itinerary than almost any other transatlantic journey I cover. Business class from Tucson to Valencia always involves at least one connection, and the smartest version of this trip routes through Dallas-Fort Worth or Phoenix on American, then transfers to a transatlantic partner for the long-haul segment into Madrid or London before a short intra-European hop down to Valencia. American Airlines operates the domestic and sometimes transatlantic legs with its Flagship Business seats on select widebodies, while British Airways brings its Club Suite—a fully enclosed, direct-aisle-access product—onto its Heathrow-bound flights, and Iberia's A330 and A350 business class cabins, with their staggered lie-flat seats, are the natural finishing touch for anyone connecting through Madrid.
Having flown this corridor repeatedly, I've learned that Madrid-Barajas is the more forgiving connection point for Valencia-bound travelers, since Iberia's short domestic hop to VLC departs from the same terminal complex as most of its long-haul arrivals, sparing you the security-and-transfer marathon that London Heathrow can impose if you're routing through BA. If Heathrow is unavoidable, build in at least two hours, since Club Suite passengers still funnel through the same congested T5 transfer security as everyone else. My insider tip: book the Iberia-operated final segment separately when possible, as Iberia often prices Madrid-Valencia business seats surprisingly leniently as an add-on to an international premium ticket, even outside published fare bundles.
April, May, September, and October remain the sweet spot for this routing—shoulder season keeps Valencia's Fallas crowds or summer heat from complicating your trip while airfares soften industry-wide on the Spain corridor. Given how much these connecting itineraries fluctuate week to week, setting up fare alerts is the only reliable way to catch a premium seat before it disappears.