Deserialize data: analyze how it's compiled your exe (try File Analyzer). Try to deserialize the binary data with the language discovered. Then serialize it in a xml format (language-indipendent) that every programming language can understand
Analyze the binary data: try to save various versions of the file with little variation and use a diff program to analyze the meaning of every bit with an hex editor. Use it in conjunction with binary hacking techniques (like How to crack a Binary File Format by Frans Faase)
Reverse Engineer the application: try getting code using reverse engineering tools for the programming language used for build the app (found with File Analyzer). Otherwise use disassembler analysis tool like IDA Pro Disassembler