Alcohol-initiated ROPs ofl-lactide were performed in bulk at 160 °C for 72 h with variation of the catalyst or with variation of the initiator (aliphatic alcohols). Spontaneous crystallization was only observed when cyclic Sn(ii) compounds were used as a catalyst. Regardless of initiator, high melting crystallites with melting temperatures (Tm) of 189-193 °C were obtained in almost all experiments with Sn(ii) 2,2′-dioxybiphenyl (SnBiph) as catalyst, even when the time was shortened to 24 h. These HTmpoly(lactide)s represent the thermodynamically most stable form of poly(l-lactide). Regardless of the reaction conditions, such high melting crystallites were never obtained when Sn(ii) 2-ethylhexanoate (SnOct2) was used as catalyst. SAXS measurements evidenced that formation of HTmpoly(l-lactide) involves growth of the crystallite thickness, but chemical modification of the crystallite surface (smoothing) seems to be of greater importance. A hypothesis, why the “surface smoothing” is more effective for crystallites of linear chains than for crystallites composed of cycles is discussed.