Blends of poly(methyl-n-propylsilane) (PMPrS) and poly(di-n-hexylsilane) (PDHS) were prepared in various compositions by solution mixing method. The blends were studied using differential scanning calorimetry, optical microscopy, fluorescence and UV spectroscopy. The blend samples were isothermally crystallized at temperatures in which only the PMPrS crystallized. The equilibrium melting point of PMPrS was estimated from the Hoffman-Weeks plots. Depression of equilibrium melting point of PMPrS with increasing PDHS content indicated some degree of miscibility. Fluorescence spectroscopic studies indicated that energy transfer occurs form PMPrS to PDHS. Comparison with an immiscible blend showed that energy transfer occurs only in miscible blends. Optical microscopy studies using crossed polarizers showed liquid crystalline mesophase in all the blends with PMPrS/PDHS = 90/10-0/100.