Though you can upload objects to S3 with sizes up to 5TB, S3 has a size limit of 5GB for an individual PUT operation.
In order to load files larger than 5GB (or even files larger than 100MB) you are going to want to use the multipart upload feature of S3.
http://docs.amazonwebservices.com/AmazonS3/latest/dev/UploadingObjects.html
http://aws.typepad.com/aws/2010/11/amazon-s3-multipart-upload.html
(Ignore the outdated description of a 5GB object limit in the above blog post. The current limit is 5TB.)
The boto library for Python supports multipart upload, and the latest boto software includes an "s3multiput" command line tool that takes care of the complexities for you and even parallelizes part uploads.
https://github.com/boto/boto