There's no better way to learn than by doing. Assuming we're talking about basic web-development here for people with limited prior knowledge, I would design the syllabus around a final goal of building a fully-functioning website. Better yet: have a really specific goal. Maybe decide that the website should be a one-page online store. This makes it easy to split the syllabus up into smaller, manageable chunks and everyone will know what they're shooting for, even if some pieces get a bit tricky. Also, this way they only get the stuff they need. Let's be honest, nobody cares about the theory behind web development.

I would start with registering a domain name, setting up hosting and DNS, creating and modifying the index.html file. Then add a css file and run through the basics of html and css standard practices. Limit the design to basic colors and fonts at first. Just when they start to get the hang out it, bust out a crash course in web design with Adobe Illustrator and make those sites pretty. After that, utilize something like Paypal's webmaster tools to set up an extremely simple shopping cart. If time allows, dedicate a session to Jquery UI to spice up the sites even more. In the end, there will be some really polished final products with plenty of new skills and lots of invaluable experience.

That's what I'd do. Good luck!