Irrespective of using NodeJS or io.js, the answer should be the same. You're going to start an express application and start it.
Assuming you've installed io.js already, on the command line type:
#install a generator for the express
npm install express-generator -g
application
mkdir my-application-folder
cd my-application-folder
#use the express generator to generate a new application
express
#now install node_modules from package.json
npm install
and once you've got the files, you can start the application with:
npm start
So this should start the application, irrespective of it being nodeJS or iojs.
However, if you're starting out with Node/io and you're looking to make this your webserver, be aware there are a number of add-ons and setting tweaks which are required before an application is suitable for production. See here and here, for example