Python fundamentals include character sets, tokens, literals, operators, and the overall program structure. The character set includes letters, digits, symbols, and whitespace. Tokens are the smallest units like keywords, identifiers, literals, operators, and punctuators. Literals represent values like strings ("Hello"), numbers (10), Booleans (True/False), and None. Operators perform actions on operands like arithmetic (+,-), relational (==), and assignment (=) operators. A Python program structure uses statements, functions, comments, indentation to define blocks, and can call functions.