There is no diode across VDD and VSS, but there are so called parasitic diodes at the GPIOs. But these parasitic diodes arise as a by-product during production of the die and must not be used as a diode.
Please explain your expectations, maybe we can sort that out.
/Peter
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FWIW, on my STM32F4 disco board, my multimeter shows 0.378V when connected between GND and VDD. I assume it's grabbing the voltage protection diode voltage.
I agree it's an odd measurement to make.
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