Additively manufactured parts produced via laser powder bed fusion (LPBF) have limitations in their applications due to post-processing requirements caused by high surface roughness. The characteristics of side-skin surfaces are generally assumed to be dominated by adhered powder particles. This work aims to analyze and interpret the effects of LPBF processing parameters on side-skin surfaces. As such, this work has two sections to investigate the effect of (i) core and (ii) border LPBF parameters on side-skin surface roughness for Ti–6Al–4V. The findings show that there is a robust correlation between both core and border LPBF parameters on side-skin surface morphologies. In terms of core LPBF parameters, an interaction between laser power and beam velocity is shown to influence side-skin surface roughness, resulting in Sa values in the range of 11–26 μm. Additionally, a preliminary investigation into the effect of melting mode phenomena at the border leads to a possibility of obtaining Sa values of <10 μm, with reduced effects of adhered and partially fused powder.