Combining ability along with heterosis was elucidated in the 21 F1 hybrid population of rice derived from a 7 × 7 diallel mating design. Furthermore, to formulate a strategy for marker-based prediction of heterosis, the molecular genetic diversity (GD) was then surveyed among the seven parental lines with RAPD markers. Analysis of combining ability revealed significant GCA and SCA variances and the ratio between the aforesaid genetic parameter was more than unity for most of the traits signifying the preponderance of additive gene action. Hybrid combination Double Rice × Pokkali was the best specific combiner for the traits pollen fertility percentage (%), panicle length (cm), filled grains/panicle (no.) and grain yield/hill (g) while Muktagacha × BRRI dhan29 and Basmati × Double Rice were the best specific combiners for grain length (mm) and 1000-grain weight (g), respectively. Regarding the magnitude of heterosis, Double Rice × Pokkali exhibited maximum heterobeltiosis for panicle length (33.33%) and the number of filled grains/panicle (144.01%). Furthermore, Pokkali × Chinigura was verified for producing the highest heterobeltiosis for tillers/hill (173.17%), as well as grain yield/hill (71.05%). The heatmap relying on molecular genetic diversity exposed the highest genetic distance between Chinigura and Pokkali followed by Muktagacha and Pokkali. Unweighted neighbor-joining trees clustered the parental lines into three groups indicating the presence of considerable genetic diversity among those seven parental genotypes. A positive and significant correlation was explored between molecular GD with specific combining ability as well as heterosis for all of the traits revealing the huge potentiality of hybrid performance prediction using RAPD markers with the present set of individuals. Thus, exploration of definite genomic regions underlying the candidate genes for respective traits relying on such RAPD-generated data following an advanced molecular marker approach would pave the path of mining out yielder heterotic combinations.