Madrid is an excellent jumping-off point for exploring other historically significant sites. The massive monastery of El Escorial is probably the best destination if you want to stick close to Madrid, but the high-speed train makes it easy to venture farther, to two destinations that should be on everybody's list: Toledo and Segovia. Other options worth exploring are Ávila (1½ hours away by AVE) and Salamanca (2½ hours away by AVE). Any of these four destinations make great day trips, except Salamanca, for which you really need an overnight to experience fully; Toledo would optimally get an overnight as well, but you can do it in a day if time is limited.
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