From the Struct documentation:
A Struct  is a convenient way to bundle a number of attributes together, using accessor methods, without having to write an explicit class. 
On the other hand, a Hash:
A Hash  is a collection of key-value pairs. It is similar to an Array, except that indexing is done via arbitrary keys of any object type, not an integer index. The order in which you traverse a hash by either key or value may seem arbitrary, and will generally not be in the insertion order. 
The main difference is how you access your data.
ruby-1.9.1-p378 > Point = Struct.new(:x, :y)
 => Point 
ruby-1.9.1-p378 > p = Point.new(4,5)
 => #<struct Point x=4, y=5> 
ruby-1.9.1-p378 > p.x
 => 4 
ruby-1.9.1-p378 > p.y
 => 5 
ruby-1.9.1-p378 > p = {:x => 4, :y => 5}
 => {:x=>4, :y=>5} 
ruby-1.9.1-p378 > p.x
NoMethodError: undefined method `x' for {:x=>4, :y=>5}:Hash
    from (irb):7
    from /Users/mr/.rvm/rubies/ruby-1.9.1-p378/bin/irb:17:in `<main>'
ruby-1.9.1-p378 > p[:x]
 => 4 
ruby-1.9.1-p378 > p[:y]
 => 5 
In short, you would make a new Struct when you want a class that's a "plain old data" structure (optionally with the intent of extending it with more methods), and you would use a Hash when you don't need a formal type at all.