Why do indexes in XPath start with 1 and not 0?

Array and other collection indexes represent memory offsets, so logically enough they begin at zero. XML and XPATH indexes represent positions and counts, so logically enough they begin at one (and zero is therefore representative of "empty")

To answer this question, we must examine the history of some technologies.

RSS XML XSLT and XPath History

Version 0.9 of RSS was originally released as RDF Site Summary in 1999 by a couple of guys at Netscape for Netscape’s my.netscape.com portal. Later that year, it was renamed to RSS (Rich Site Summary) with the v0.91 update. Development of the project changed hands several times, but RSS version 1.0 was released by December of 2000. With the v1.0 update, RSS included support for XML.

During 2002 v2.0 was released in September as RSS (Really Simple Syndication) and began to evolve into a major internet technology. In it’s early history, RSS feeds (and the XML data they contained) were read by humans in the raw format. Blogs and other news sources used RSS feeds and XML to output continuously updated information. Since XML was being read by mere mortals (non-programmers), XPath and XSLT also needed to be easily understandable, so that these mere mortals would not be overwhelmed by complexity when interacting with it. That is why XPath mimics the style of URIs, which is something that end-users were already familiar with. One of the concessions made for the purpose of readability by users, was to use old-fashioned numbering techniques i.e. 1-based indexes instead of 0-based indexes. That is the same concession that you mentioned with VBScript, and it was made for similar reasons.

Although RSS feeds and XML were made to be readable for most people, RSS readers were developed to provide a more pleasant interface for humans to read RSS feeds. Now, raw RSS and XML data are read almost exclusively with some sort of reader or graphical interface. XML is still in frequent (perhaps permanent) use across the web, but it is masked by fancy graphical user interfaces to provide a better experience for end users.

*The term, "mere mortals," refers to humans who are not programers