als
than
Used for comparisons after a comparative, for example bigger, faster, better.
Mein Bruder ist älter als ich.
My brother is older than me.

than / when / as
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than
Used for comparisons after a comparative, for example bigger, faster, better.
Mein Bruder ist älter als ich.
My brother is older than me.

After a comparative form, such as 'größer' (bigger), 'besser' (better), or 'schneller' (faster), 'als' (than) is always used for the comparison. The nouns or pronouns being compared stand in the same case.
Ein Elefant ist viel größer als eine Maus.
An elephant is much bigger than a mouse.
As a temporal conjunction, 'als' (when) introduces a subordinate clause that describes a one-time event in the past. The conjugated verb stands at the end of the clause.
Als ich jung war, gab es noch keine Smartphones.
When I was young, there were no smartphones yet.
To describe the profession, role, or function of a person or thing, German uses 'als' (as) followed by a noun in the nominative. With job titles, usually no article is used.
Er arbeitet seit fünf Jahren als Ingenieur.
He has been working as an engineer for five years.
The phrase 'als ob' (as if) introduces an unreal comparative clause, which usually uses Konjunktiv II. The verb stands at the end. A shorter variant is 'als' + Konjunktiv II verb at the beginning of the subordinate clause.
Er redet so, als ob er der Chef wäre.
He talks as if he were the boss.
The fixed expression 'sowohl … als auch' (both … and) is a two-part conjunction. It connects two equivalent parts of a sentence and means something like 'and also'.
Das neue Restaurant bietet sowohl Fleischgerichte als auch vegane Speisen an.
The new restaurant offers both meat dishes and vegan meals.
After a comparative, for example 'älter' (older) or 'besser' (better), 'als' (than) must be used for the comparison. Using 'wie' (like/as) here is a common mistake in colloquial speech, but it is not correct in standard language.
Dein Koffer ist schwerer als meiner.
Your suitcase is heavier than mine.
and
'und' and 'als' can both connect two equivalent things in certain expressions. Normally, you simply use 'und' for this: 'Tee und Kaffee' (tea and coffee). 'als' only fits here in the fixed construction 'sowohl ... als auch' (both ... and). This form emphasizes more strongly that both things really apply. Learners may confuse the words because 'sowohl ... als auch' works similarly to 'und'. On its own, however, 'als' cannot simply replace 'und'.

Am Bahnhof sind heute sowohl Busse als auch Züge verspätet.
At the station today, both buses and trains are delayed.
Greta hat im Zug ihr Handy und den Laptop benutzt.
Greta used her phone and laptop on the train.