Results of optical and electrical measurements on Ni&sngbnd;P films are presented, in both as‐deposited and annealed films. The films range in thickness from 100 Å to 1 mm and vary in composition from 0%–16% P by weight. The results suggest a model for the structure of these films. For freshly deposited films, the model consists of a three‐dimensionally aggregated liquid‐like structure with nonmetallic properties. Heat treatment is shown to create a packing tendency followed by crystallization of the films at a relatively high temperature (around 350°C). This results in a nearly metallic film behavior.