Nano-crystalline and amorphous Co-P coatings were deposited on plain carbon steel substrates by using direct current. Effects of electrolyte pH on morphology, current efficiency, phosphorus content, hardness, and preferred orientation of the nano-crystalline coatings were investigated. Moreover, the effects of heat treatment on microstructure and hardness of the nano-crystalline and the amorphous coatings were studied. The results showed that, phosphorus content and hardness of the nano-crystalline coatings were decreased by increasing of the pH, in spite of a current efficiency enhancement to as much as 98%. Grain size and preferred orientation were also changed from 13 to 31 nm and from mostly [002] to [100] by increasing the pH from 1 to 4, respectively. Smoother coatings and higher current efficiencies were obtained by the addition of 1 g/L sodium dodecyl sulfate (SDS) to the bath. Highest hardness of the nano-crystalline and the amorphous coatings was about 600 and 750 HV, which increased and reached 760 and 1090 HV after heat treatment, respectively.