Inorganic Mg2+ and Al3+ containing layered double hydroxide (LDH) particles were synthesised in situ from aqueous solution onto chemical pulp fibers of pine (Pinus sylvestris). High super saturated (hss) solution with sodium carbonate produced LDH particles with an average diameter of 100–200 nm. Nano-size (70 nm) LDH particles were found from fibers external surface and, to a lesser degree, from the S2 cell wall after synthesis via low super saturated (lss) route. The synthesis via slow urea hydrolysis (Uhyd) yielded micron and clay sized LDH (2–5 μm) and enabled efficient fiber densification via mineralization of S2 fiber wall layer as indicated by TEM and compliance analysis. The Uhyd method decreased fiber compliance up to 50%. Reduction in the polymerisation degree of cellulose was observed with capillary viscometry. Thermogravimetric analysis showed that the hybridization with LDH reduced the exothermic heat, indicating, that this material can be incorporated in flame retardant applications. Fiber charge was assessed by adsorption expermients with methylene blue (MB) and metanil yellow (MY). Synthesis via lss route retained most of the fibres original charge and provided the highest capacity (10 μmol/g) for anionic MY, indicating cationic character of hybrid fibers. Our results suggested that mineralized fibers can be potentially used in advanced applications such as biocomposites and adsorbent materials.