Valencia remains one of the more rewarding puzzles in transatlantic premium travel precisely because no carrier flies there nonstop from Chicago—there is no such thing as a direct business class from Chicago to Valencia, so the routing itself becomes part of the strategy. My preferred path after dozens of iterations is American Airlines' nonstop ORD–LHR service in Flagship Business, connecting onto British Airways for the short LHR–VLC hop, which keeps you within the Oneworld ecosystem and lets you clear security once in Chicago rather than juggling two separate check-ins abroad. Iberia offers an alternative through Madrid, and if your dates align with their widebody rotations, the A330 or A350 business cabin with proper lie-flat seats and Iberia's Madrid lounge access makes for a smoother final leg into VLC than the regional jets sometimes used on the BA-via-Heathrow routing.
The Heathrow connection deserves respect rather than dread—Terminal 5, where both AA and BA operate, is efficient if you allow at least 90 minutes given its scale, and I always request early lounge access to shower before the final leg, since a 10-hour transatlantic overnight followed by a short daytime hop can leave you looking worse than you feel. Madrid-Barajas, by contrast, rewards travelers who fly Iberia's own metal end to end, as their T4 hub was purpose-built for exactly this kind of connection and rarely induces the gate-sprint anxiety Heathrow can produce during peak summer congestion. April, May, September, and October consistently deliver the best combination of fare value and pleasant Valencian weather, avoiding both the August heat and the winter lull when frequencies thin out.
One tip most guides miss: Iberia's Madrid-routed itineraries often price more competitively in business than the Heathrow alternative during shoulder season, even though the AA transatlantic product is arguably superior—so it pays to compare both routings rather than defaulting to the "obvious" hub. Given how these fares fluctuate week to week across three different carriers and two competing hub strategies, setting up automated fare alerts for this specific city pair is the only realistic way to catch the moments when premium inventory briefly opens at attractive levels.