Windows Disk Cleanup: "Compress old files" option
Selecting this option basically compresses all old DLL and SYS files in the Windows folder that hasn't been accessed recently or ever. It uses the normal built in NTFS compression, and to be very honest on today's hard-drives has little or no impact on the folder sizes. These files already take up minimal space.
The How-To Geek has an article here describing how to tweak it. The more precise description from the The Elder Geek here is:
Unlike the other categories, Compress Old Files doesn't delete any files from the drive. It compresses files that Windows hasn't accessed for a specified period of time. The files are still available, but there will be a slight increase in access times because the files will be decompressed the next time they are accessed. Note that when Compress Old Files is highlighted an Options button appears. Clicking it will allow you to set the number of days to wait before an unaccessed file is compressed.
To answer the second part of your question, NTFS compression is reasonable if your storing a lot of data like Music, Documents and Videos and should NOT be enable on your OS drive. If you have a second drive just for storage it can be enabled, however the compression ratios are extremely small. You will not see 100GB's of space saved using this feature, and it is not as compact as zipping the files for example.
Among others, SQL Server does not allow it's database to be stored on NTFS compressed volumes as the performance on decompression is extremely expensive.
It may have little impact on free space, but in this day and age the disparity between processor speed and disk speed is so great that turning compression on is a no-brainer. The access will in most cases be faster than access to files with no compression. The only exception is very small files and files that are compressed anyway, such as ZIP or MP3.
You will probably not notice any speedup, though, because the option in question concerns only DLLs and system files that have not been accessed recently (so it's a good bet you won't need them in the future either). You have a better chance of actually having a faster computer by compressing everything.
Pro - you save space.
Con - when you access those files they need to be decompressed, so access is slower.
Should you? As always, it depends. You need to consider how often you access "old" files and whether (slightly - it depends on your machine) a slow down in the access of these files matters to you, but the most important factor is probably how great your need of the spare disk space is.