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The bus station is called Estacion Sur de Autobuses de Madrid. There are more than 50 bus companies that operate from this station and have buses to every province in Spain and to other cities in Europe.
Estacion Sur de Autobuses de Madrid
Calle Mendez Alvaro, 83
To reach the station by bus:
Lines 8 , 37 , 58 , 102 , 113, 148 y 152.
To reach the station by Trenes de Cercanías: Méndez Álvaro.
To reach the station by Metro: Méndez Álvaro.
Example of How To Look for Schedules to Avila:
The website is only in Spanish, but here is an example of how to navigate the website.
1. Click on Horarios Nacionales.
2. You go to the Salidas de Madrid page.
Provincia de destino (Province of destination) - Choose Avila.
Poblacion de Destino (Town of destination) - Choose Avila.
Fecha de Salida (Departure Date) - Choose ninguna (none).
Click on Buscar button (Find).
3. One finds the schedule and the only bus company is Larrea, S.A.
Use a similar procedure for international destinations (Horarios Internacionales).
There is a transportation hub (Intercambiador) at Avenida de América where buses leave for Burgos, Santander, Vitoria, Bilbao, San Sebastián, Soria, Pamplona, Logroño, Granada y Guadalajara, and also a line Madrid-Zaragoza-Barcelona of the bus company called ALSA. There are vending offices for ALSA and Continental (now belonging to the ALSA group). Consult the Movelia website.
The buses going to Segovia leave from Principe Pio, the metro stop that also has the bus stop for Segovia. There is a vending office in the underground area of the metro for the La Sepulvedana going to Segovia, so one does not have to go to the street.