Al(OH)3 nanoparticles (ATH NPs) and phosphorylated cellulose nanofibrils (PCNFs) were used as user-friendly and comfortable coating components on flame-retardant fabric to improve its thermophysiological comfort and high-intensive heat protection properties. The effect of the PCNF imprinting and its attachment after the post-printing of a hydrophobic polyacrylate (AP) on the same (back side) or the other (front) side of the fabric, with and without the addition of ATH NPs, was considered, to maintain the front side (facing the wearer) as hydrophilic while keeping the back side (facing the outside) hydrophobic. The amount of coatings applied and their patterning were studied, varied with the ATH NPs’ concentration (1.7, 3.3 and 6.7 wt%) and screen mesh size used (60 and 135), based on the coating’ mass, fabric’s air permeability, thickness and microstructure. The reduced moisture build-up (55%), increased the water vapour (13%) and heat (12%) transfer from the skin, were assessed by applying PCNF under the AP, being more pronounced in the case of using a 135 mesh-sized screen, given the smaller, more densely distributed, thinner and imprinted pattern coatings. These effects were further improved by the addition of nanoporous ATH NPs, which allowed more homogeneous spreading of the moisture and its faster transport. Such a treatment also shifted the fabric’s degradation temperature towards higher values (up to 15°C), retained up to 30% of high-heat flux (21 kW/m2), prolonged the time to ignition by 11 s and reduced the total heat released by up to 60%, thereby providing better protection when exposed to the heat, due to the presence of the phosphorous (PCNF) promoted generation of an Al2O3 char acting as a barrier layer, while also reducing the production of heat and generation of smoke by 75%.