Any time electricity flows through something a bit is dissipated as heat. (Except in something called a superconductor!) The more resistance it experiences along its path, the more energy is lost to heat. The longer, skinnier, or tougher the path the more resistance it experiences.
This is the basis of electric heater function or a coffee maker. They just provide a hard to travel path for the electric.
The wires in your wall are always live, so, when you plug in your charger you are adding more path and a tougher path to travel so more heat is lost.
Inside the charger is a really long spool of wire and some semiconductors and capacitors. They all stay on, traveled by electric, ready for you to plug your phone in.
A simple way to save money if you want to keep your charger plugged in all the time is to use switch before it like a power strip.
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