A process to deposit nanocrystalline silver particulate film by adjusting the physical/chemical parameters at liquid-liquid interface was developed. The film was transferred on a suitable substrate by Langmuir-Blodgett (LB) technique. The film was characterized by transmission electron microscopy (TEM), electron diffraction (ED) and atomic force microscopy (AFM). TEM revealed that the as-prepared film consists of partly aggregated spherical silver particles and their sizes were in the range 5-20 nm. ED shows a spot pattern, characteristic of partly aggregated material with very small crystallite size. The optical absorption of vergin and annealed films is studied. The effect of annealing is attributed to Ostwald ripening of some particles and simultaneous breaking of aggregates to smaller particles.