▶ We grew pentacene films by pulsed laser deposition. ▶ Substrate orientation controlled growth mode. ▶ Elementary cell parameters were calculated from electron diffraction measurements. Thin pentacene films were deposited on KCl and ITO/glass substrates by the pulsed laser deposition method (PLD) using a YAG:Nd 3+ laser with a second harmonic ( λ = 532 nm). We compared the structure of the layer on differently oriented substrates with respect to the pentacene plasma plume – vertical and parallel orientation. The structure of the layers formed was examined using SEM, RHEED and THEED methods. The lattice parameters of the layer deposited on KCl were determined from THEED pattern ( a = 5.928 Å, b = 7.874 Å, c = 14,98 Å, α = 76.54°, β = 75.17°, γ = 89.20°). The preferred direction 1   1 ¯   0 of the layer growth on KCl substrate was addressed. The effect of the substrate orientation results in a different growth mode of the layers.