Nanoscale additives have emerged as an effective way to improve the performance of diesel/biodiesel blends and solve problems related to blend efficiency, emissions reduction and engine performance. This review article examines the use of nanoadditives in diesel/biodiesel blends and their effects on various compounds and emissions. Combining the findings from selected case studies, this review provides deep insight into the mechanisms of nanodope interactions in oil matrices. In this article, the effects of nanoparticles on ignition properties, particle formation and exhaust emissions are examined. From a critical perspective, this review demonstrates not only the advantages of nanoadditives, but also the need for better understanding and further research to develop their use with diesel/biodiesel blends in a biogas derived compressed natural gas (BioCNG) dual fuel engine.