That would exactly be a good idea to start Electronics by programming a microcontroller. That could give you a very good understanding on how the things are going on electronics. Using the MCs, you will need to use other electronic components (e.g. capacitors, resistors, clock generators etc.) therefore that will also get you familiar with those components which are commonly used in electronics.
Use definetely PIC microcontrollers and buy (or download) a book which tells how to program them. you can easily find a PIC MC on the market by paying less than other MCs.