There are disassemblers/decompilers around BUT depending on what the program was built in you probably won't get what you expect.
For instance:
A Visual Basic coded exe file is NOT a monolithic stand alone program. The exe files are in what is known as "p-code", and mainly consist of external calls to the VB runtime library.
.NET compiled executable are the same (if not moreso). The .exe file is more of an extension of the framework than a separate entity. Though I must admit I have never attempted to decompile a third party .net exe, but I would guess it's not something you could work out howit does what it does exactly.
Even if the executable is a fully fledged, standalone, fully compiled machine code package created in C, C++, Pascal, Delphi etc. Unless you have the symbol files from the compile process all you will get is lines and lines of x86 machine code and the assembler mnemonics to go with that code.
Also included in that code will be calls to external functions, calls to windows API functions etc etc.
Now unless you are a super geek and have intimate working knowledge of the Windows OS at machine code level the chances of working out exactly what something does is pretty slim.
What you can get however, which is where I suspect your interest may lie  , is you can find the internal values and strings and the code that examines these strings and internal values to look for serial codes, registration info etc. Which can then be changed using a hex editor if you know what you are doing 
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