This articleArticle Skype's roadmap and architectureSimplified description of the Skype architecture.
Leader of Skype database teamAsko ojaHttp://www.slideshare.net/highload/asko-oja-moskva-architecture-highload-presentation said that Skype uses open source tools contributed by PostgreSQL and Skype (plproxy, pgbouncer, pgq...) for distributed databases.
Finally, you can refer to the two blogs of leader Kristo kaiv of Skype database development team for details on how to use plproxy for horizontally Scalable Distributed Databases:
PostgreSQL cluster: partitioning with plproxy (part I)
PostgreSQL cluster: partitioning with plproxy (Part II)
The presentation http://www.infoq.com/presentations/Learning-from-Five-Years-Skype of leader Andres kutt, the Skype architect team, shared some of their architectural experiences and experiences on Skype. This guy is also hard to hear in English. It is best to read this transcript: http://www.infoq.com/articles/learnings-five-years-skype-effect.