There are guys like Matthew James Taylor and David Walsh who code new and innovative interfaces and widgets - but even their sites are database driven (even maybe homegrown) CMS that they use to display their code inventions.
I write extensions for a popular CMS which make it more useful for myself and others, but an HTML/CSS only designer will have a tough learning curve to jump into that type of development as there are many languages working in concert (PHP/ASP/Java, JS, JSON, XML, SQL, INI, HTML, CSS, ???) with HTML/CSS being perhaps the least used.
Not that I couldn't, but I wouldn't hand code an entire site these days. Efficiency and productivity is the key now and you just can't compete with a modern CMS in those regards.