The syntax is:

a[start:stop]  # items start through stop-1
a[start:]      # items start through the rest of the array
a[:stop]       # items from the beginning through stop-1
a[:]           # a copy of the whole array

There is also the step value, which can be used with any of the above:

a[start:stop:step] # start through not past stop, by step

The key point to remember is that the :stop value represents the first value that is not in the selected slice. So, the difference between stop and start is the number of elements selected (if step is 1, the default).

The other feature is that start or stop may be a negative number, which means it counts from the end of the array instead of the beginning. So:

a[-1]    # last item in the array
a[-2:]   # last two items in the array
a[:-2]   # everything except the last two items

Similarly, step may be a negative number:

a[::-1]    # all items in the array, reversed
a[1::-1]   # the first two items, reversed
a[:-3:-1]  # the last two items, reversed
a[-3::-1]  # everything except the last two items, reversed

Python is kind to the programmer if there are fewer items than you ask for. For example, if you ask for a[:-2] and a only contains one element, you get an empty list instead of an error. Sometimes you would prefer the error, so you have to be aware that this may happen.

Relationship with the slice object

A slice object can represent a slicing operation, i.e.:

a[start:stop:step]

is equivalent to:

a[slice(start, stop, step)]

Slice objects also behave slightly differently depending on the number of arguments, similar to range(), i.e. both slice(stop) and slice(start, stop[, step]) are supported. To skip specifying a given argument, one might use None, so that e.g. a[start:] is equivalent to a[slice(start, None)] or a[::-1] is equivalent to a[slice(None, None, -1)].

While the :-based notation is very helpful for simple slicing, the explicit use of slice() objects simplifies the programmatic generation of slicing.

You are confusing expressions with assignment. Getting values (reading) is handled differently from setting values (writing).

Assignment (setting) re-uses syntax to specify a target. In an assignment like a[:] = ..., a[:] is a target to which the assignment takes place. Using a[:] in an expression produces a new list.

In other words: you have two different language statements, that are deliberately using the same syntax. They are still distinct however.

See the Assignment statements reference documentation:

assignment_stmt ::=  (target_list "=")+ (starred_expression | yield_expression)
target_list     ::=  target ("," target)* [","]
target          ::=  identifier
                     | "(" [target_list] ")"
                     | "[" [target_list] "]"
                     | attributeref
                     | subscription
                     | slicing
                     | "*" target

[...]

• If the target is a slicing: The primary expression in the reference is evaluated. It should yield a mutable sequence object (such as a list). The assigned object should be a sequence object of the same type. Next, the lower and upper bound expressions are evaluated, insofar they are present; defaults are zero and the sequence’s length. The bounds should evaluate to integers. If either bound is negative, the sequence’s length is added to it. The resulting bounds are clipped to lie between zero and the sequence’s length, inclusive. Finally, the sequence object is asked to replace the slice with the items of the assigned sequence. The length of the slice may be different from the length of the assigned sequence, thus changing the length of the target sequence, if the target sequence allows it.

(Bold emphasis mine).

Compare this with the Slicings section in the expressions reference documentation; slicing in an expression produces a slice() object, which the list.__getitem__ method interprets as a request for a new list object with the matching indices copied over. Other object types can choose to interpret a slice object differently.

Note that there is a third operation, the del statement to delete references, including slices. Deletion takes the same target_list syntax and asks to remove the indices indicated by a slice.

These three operations are, under the hood, implemented by the object.__getitem__() (reading), object.__setitem__() (writing) and object.__delitem__() (deleting) hook methods; the key argument to each of these operations is a slice() object, but only __getitem__ is expected to return anything.