The glass transition phenomena of binary systems consist of polyalcohols such as ethylene glycol, propylene glycol, 1,3-propanediol and glycerol were investigated by differential scanning calorimetry (DSC). For every system, composition dependence of the glass transition temperature, T-g(x), was reproducible with an empirical form, T-g(x) = [xT(g,1) + Cg(1 - x) T-g,T-2]/[x + C-g(1 - x)]. The composition dependence of T-g predicted based on the entropy theory for regular solutions agreed well with the experimental results in all systems. Excess configurational entropy, S-c(E), as deviation from the regular solution model, were very small compared to the expected entropy. The behavior of the present system as a regular solution is discussed from the viewpoint of structural change on mixing. (C) 1998 Elsevier Science B.V. All rights reserved.