All audio equipment has isolation from the mains, so there is no direct connection from the mains to the audio circuit, and there is always a transformer of some sort blocking the ac.
Whether or not the mains lead is polarised, both the live and neutral have to be regarded as possibly at mains voltage.
High power amplifiers have large voltages present, even on the audio side. An amplifier that can produce 500 W into 8 Ohms will have a peak - peak voltage of around 200 V, so there will be voltages that large on the audio side. Also there can be large capacitors which remain at dangerous voltages for some time after the mains power is removed.
Low power amplifiers and pre-amps use smaller voltages, so there isn't much danger of an electric shock from the audio side.
However, if you are measuring stuff inside audio equipment, you need to know which part is on the mains side of the transformer, and that is not always obvious. You're welcome to post a photo and someone here can say which bits are likely to be live.
Audio equipment is often made without an earth to avoid hum loops.
https://en.wikipedia.org/wiki/Ground_loop_(electricity)
There is no danger of injury if you ground the chassis of audio equipment, possibly via the ground lead of a grounded oscilloscope. There is a possibility of a mains hum but that will have little effect on fault-finding.
In my experience, all mains powered oscilloscopes have the BNC grounds connected to mains ground.