VTT is less widely accepted than SRT by desktop players and editors. ASS gives full control over how subtitles look. VTT is at home in captions on web pages and in HTML video players; ASS is the usual choice for anime and karaoke subtitles with fonts, colours and positioning.
The text is read as UTF-8 or UTF-16, whichever the file is. An older file in another code page is read using the charset it declares, or as Windows-1252 if it declares none, so accented letters in an unlabelled legacy file can come out wrong. A file that is not text, such as the picture-based subtitles of a DVD, is refused instead of being converted to nonsense. Of the styling, only italic, bold, underline and the position on screen (top, middle or bottom, left, centre or right) travel between formats; fonts, colours, outlines and effects do not. WebVTT comments, STYLE blocks and region definitions are skipped; the cues, their text and positions are kept. The file is written with a single Default style (Arial, white with a black outline) that the player or Aegisub can restyle, and times are rounded to hundredths of a second, the precision ASS has.