In the present investigation, Ti-6Al-4V ELI samples were manufactured by the powder-bed fusion (PBF) process using the laser sintering (LS) technology. Microstructure, chemical and phase constitution, and mechanical properties were studied by means of the transmission electron microscopy, atom probe tomography, X-ray diffraction, nanoindentation and mechanical testing. It was found that the structure of LS samples consisted of two different variants of metastable phases, namely the hexagonal alpha' martensitic phase and small amounts of the orthorhombic alpha '' martensitic phase. The martensitic alpha'-phase was formed because of the high cooling rates of the LS method, The {10 (1) over bar2} <(1) over bar 011 > hexagonal martensite tensile twins were observed in the microstructure of the as-build alloy. Small areas with inner twinning martensitic plates, which are typical for the metastable orthor-hombic martensitic phase in titanium alloys, were identified by the transmission electron microscopy. Atom probe tomography (APT) confirmed localization of beta-stabilizing elements at interfaces, presumably at the twin or lamella boundaries. The structure and origin of the martensitic phases in 3D printed Ti-6Al-4V alloys are discussed with respect to in-situ heat treatment during manufacturing.