The Alpine Triassic units of Switzerland, Northern Italy and Western Austria offer an extensive geological archive, in which the enigmatic process of dolomite formation can be studied in a palaeoenvironmental context. Recent studies clearly demonstrate that large amounts of the Alpine Triassic dolomites are late diagenetic or hydrothermal. Nevertheless, as part of multiple generations of diagenetic overprint, some generations of fine-crystalline, Ca-rich dolomite appear strictly confined to their depositional facies and show signs of very early formation at surface temperatures in specific ancient depositional environments. In this review, three cases of Alpine Triassic dolomites are discussed, where dolomite rocks may have formed during or soon after sedimentation. The sedimentary facies indicate contrasting palaeoenvironmental conditions and, hence, document three different possible processes of dolomite formation: (i) In the Dolomite Mountains (Northern Italy), dolomite beds of the partly isolated Middle Triassic (Anisian/Ladinian) Latemar Platform are confined to the very top of shallowing-upward lagoonal facies cycles. (ii) Dolomite beds of the San Giorgio Basin (Southern Switzerland), an intra-platform basin that opened during the Anisian/Ladinian transition, are associated with organic carbon-rich shales, which were deposited in a deeper water environment under anoxic conditions. (iii) In the entirely dolomitized platform facies of the Dolomia Principale (Hauptdolomit Formation), a very early generation of fine-crystalline dolomite occurs in the shallowest part of evaporative peritidal cycles. This platform extended over thousands of square kilometres along the Tethys margin during the Late Triassic (Carnian and Norian) and large amounts of carbonate were deposited under hypersaline sabkha-like conditions. Representing three distinct depositional environments, these three different Triassic systems show features in common with several dolomitization models developed from the study of modern dolomite-forming environments; for example, the sabkha model, the evaporative lagoon/lake model, the organogenic model and the microbial model. Although these actualistic models may be applicable to reconstruct the palaeoenvironmental conditions during dolomite formation, dolomite-forming processes during the Triassic were apparently quite different from the modern world in terms of distribution and scale. Recent developments in stable-isotope geochemistry and high-resolution geochemical probing offer the possibility to make better reconstructions of Triassic palaeoceanographic conditions and suggest a non-actualistic approach to better understand dolomite formation during the Triassic.