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Hotkey assignment instructions are found under Help in Wings3D.

The option to assign hotkeys to commands was welcomed by most (all?) people, as this allows the user to access frequently used commands etc via keystrokes, rather than having to use the contextual menu system via RMB.

In default (as downloaded) state, many (but not all) Wings commands can be assigned to a hotkey and certain existing hotkeys (coded within Wings, eg T) cannot be re-allocated without some further work.

The majority of key options (already assigned to Wings functions by default) may be re-assigned to user chosen commands however and vice versa.
If the user deletes their choice of command assigned to a Wings default hotkey, however, then that key will revert to accessing its original Wings function (upon re-opening)

Eg Suppose you assign F1, F2, F3 to View -> XYZ (having decided you don't like the default keys XYZ ) After some time you decide you do prefer the defaults - deleting your own options and re-starting Wings will return keys XYZ to their original functions - having to specifically re-assign these keys isn't necessary.
The choice of which command to assign to which key is a personal matter - one person's  'ideal' configuration often seems totally illogical to others - however, several (general) comments.

1). The same key can be assigned to the same command (Move | Free, say) across all 4 selection modes - verts, edges, faces and objects. Whilst the user has to actually 'do' the assign operation separately for each of these selection modes, it is a small price to pay for the end result - one key to move free, irrespective of what feature is actually selected on screen.

Eg User selects a vert on model, highlights Vert | Move -> Free, presses Insert and assigns M (say). Then select an edge, highlight Edge | Move -> Free, Insert and assign M (again). This operation is repeated for the other 2 modes.

Since the above procedure can also be done with all 5 move commands (XYZ, Normal, Free). The user can thus have access to 19 move commands (no Move Normal in object mode) on the same 5 keys (for instance)

Similar approaches using modifier keys, Alt / Shft / Cntrl etc, in conjunction with a key for Scale / Rotate / Extrude (or vice versa) etc can also provide similar benefits.

2). If you intend using certain commands a lot (Weld or Loopcut, say) it would make sense to assign this to a 'prime' (single action) key - rather than a configuration like Alt+Shft+Cntrl + B/L ?

3). Choosing keys on an ergonomically comfortable basis makes a lot of sense - ie Right handed mouse users setting up hotkey layouts / configurations around the LH side of the keyboard - as well as bearing in mind the span available from one hand.

4). Using hotkeys to access certain commands 'inside' other procedures / methods is useful if you want to minimise disruption to your workflow when using the 'main' command.

eg Using a piece of (previously selected and stored) geometry during a vector definition procedure.
Assigning Store / Recall | Selection to hotkeys will allow you to quickly save a selection - and just as important - recall it when needed, within a vector definition procedure.
(This is especially useful if you need to access a feature that becomes 'hidden' during the operation - like the 'source' face in a Put On op - to do a vector rotate on the object about its face normal, say.)
(Note that Store / Recall | Selection now deals with unique selections for each of the 4 selection modes - so the correct selection mode has to be operating to allow Recall to produce the required (stored) selection.)

Hotkey assignments will be saved into Wings prefs and will thus be transferred to the latest Wings release when you update. (I always de-install previous before installing new).

Since there is (currently) no means of checking hotkey assignments, there is always the possibility that the same key (combination) will be used for more than one command - if you seem to be getting some weird anomolies associated with hotkeys, it's well worth inspecting the prefs file (eg in Word), editing as necessary and saving this amended version.    

Copying the preferences file and keeping it safe somewhere else is an option worth considering - especially if you're experimenting with different setups.
This way, should something unforseen happen (and it does) and you end up losing the prefs you've spent ages 'sorting out' - then all is not lost.

At the end of the day, however, the choice is yours - if you allocate your hotkeys to commands in order that a fly lands on them - and grow to like that (probably) random layout, so what if no-one else can make any sense of it?