Each preposition in Esperanto has its own fixed meaning and only few of them are used for more relations (mostly in temporal and local meaning and preposition de).
E.g. al – to, anstataŭ – instead of, antaŭ – before, apud – next to, ĉe – near, ĉirkaŭ – around, da – of (with quantity), de – of, dum – during, ekster – outside of, el – from within, en – in, ĝis – till, inter – between, among, kontraŭ – against, krom – besides, kun – with, malgraŭ – in spite of, per – per, po – at rate of, por – for, post – after, pri – about, pro – for, because of, sen – without, sub – under, super – above, sur – on (position), tra – through, trans – across
E.g. al Praha – to Prague, en la ĝardeno – in the garden, per la martelo – using the hammer, sur la tablo – on the table, de la patro – from father

In cases where no existing prepositions can be logically used, preposition je should be used. Preposition je has no concrete meaning.
E.g. je la tri horo^H – at three o’clock, krei je Dio – trust in God, esti je kvar jaroj pli aĝa – to be four years older

Except these simple prepositions, there are also complex prepositions (prepoziciaĵoj). They are formed mostly by adverb and another preposition.
E.g. dank’ al^[25] – by virtue of, thanks to, proksime al – near to, rilate al – relating to, kompare kun – comparing with, kontraste kun – in contrast with, kune kun – together with, etc.

1) nominative-prepositive – preposition + noun in nominative
This is the most often case, e.g. sur la tablo – on the table
2) prepositive-prepositive – preposition + preposition + noun
This case is used, when it is necessary to express some move (spatial or temporal) from, to, over, etc. some place already expressed by some preposition. It is necessary to use two prepositions. The second preposition makes a prepositive with the noun and the first relates to this whole phrase. The second preposition expresses a position (spatial or temporal) and the first express an move relative to the complex of the second preposition together with the noun. E.g. el sub la lito – from under the bed
3) accusative-prepositive – preposition + noun in accusative
The accusative in this case is used to express a move^[26]. It can be replaced by second case using preposition al: sub la liton = al sub la lito – under the bed (direction).
Li iras en la domon. – He goes to the house.
Veturi ekster la urbon. – Drive out of the town.
It is beyond the scope of this grammar overview to explain meaning and usage of all prepositions of Esperanto, as a good source, I can recommend PMEG – maqvor.html and PIV.

^[25] This is the only case of elision of an adverbial e.
^[26] For overview of accusative usage, see chapter 5.1.