New time-resolved optical spectroscopic echelle observations of the nova-like cataclysmic variable RW Sextantis were obtained, with the aim to study the properties of emission features in the system. The profile of the H_alpha emission line can be clearly divided into two (`narrow and `wide) components. Similar emission profiles are observed in another nova-like system, 1RXS~J064434.5+33445, for which we also reanalysed the spectral data and redetermined the system parameters. The source of the `narrow, low-velocity component is the irradiated face of the secondary star. We disentangled and removed the `narrow component from the H_alpha profile to study the origin and structure of the region emitting the wide component. We found that the `wide component is not related to the white dwarf or the wind from the central part of the accretion disc, but is emanated from the outer side of the disc. Inspection of literature on similar systems indicates that this feature is common for some other long-period nova-like variables. We propose that the source of the `wide component is an extended, low-velocity region in the outskirts of the opposite side of the accretion disc, with respect to the collision point of the accretion stream and the disc.