On the same 65.000 € gross, a worker takes home roughly £6,951 more per year in United Kingdom than in Spain. That gap reflects the tax structure alone — before rent, healthcare, or savings behaviour come into play.
Housing is the first multiplier. Spain has moderate rent pressure, while United Kingdom has high rent pressure. That keeps United Kingdom's nominal advantage closer to a real-world advantage.
Healthcare and pensions go in the opposite direction. Spain runs a universal healthcare model — Universal public healthcare via the SNS; private cover is widespread. United Kingdom uses a universal model — NHS provides universal care funded from general taxation, with private top-ups. The country with lower take-home often shifts costs that the other country leaves to your private budget.
Net-of-everything, a relocation decision should weigh strong public welfare in Spain against strong public welfare in United Kingdom, plus differences in pension capture, social safety nets, and city-level cost of living.