Maintaining satisfactory moisture content in concrete during its early ages is very important to develop required properties. Retaining free water of the mixture for a longer period will have a beneficial effect similar to that of curing. Self-curing mixtures will be very beneficial especially in regions where water is not adequately available. Polymers in concrete have received considerable attention over the past two decades. This study investigates using laboratory synthesized water-soluble polymers: polyethylene glycol (PEG) and polyacrylamide (PAM) as self-curing agents and its effect on the degree of hydration, water absorption, permeable pores and microstructural characteristics of Portland cement mixtures without and with 8% silica fume replacement. Portland cement mixtures including PEG or PEG+PAM as self-curing agents showed a better quality compared to that of the non-cured mixtures. Mixtures incorporating 8% silica fume including a mixture of PEG and PAM as self-curing agent had a better quality compared to that of the mixture including only PEG especially at later ages.