The one-pot production of a relevant chemical such as 1,5-pentanediol (1,5-PDO) from sustainable sources (furfural) is a key reaction to compete with existing fossil sources. This work provides new evidence on the influence of the starting reagent, the features of layered double hydrotalcite (LDH)-derived catalysts in the form of mixed metal oxides (MMO) and of reaction conditions on the productivity of 1,5-PDO under batch conditions. Unlike reported studies, these results suggest the direct pathway through furfuryl alcohol intermediates, allowing the one-pot production from furfural at lower temperature than analogous systems. Productivity is maximized when Co2+ species partially substitute Mg2+ species in parent LDH, yielding promising pentanediol yields under mild reaction conditions. MMOs containing Co2+ sites show marked differences compared to analogous bivalent metals, which is here attributed to the position in which reaction intermediates such as furfuryl alcohol are adsorbed onto surface specie. This is consistent with characterized surface species by XRD, temperature programmed reduction under H2, and chemisorption experiments using CO or CO2 as probe molecules, indicative of a proper balance between metal and basic sites onto MMOs. The reported data aim to provide new reaction evidence to contribute into the search of sustainable 1,5-PDO sources.Graphical