The molecular conformation and melting behavior of triblock position isomers H(CH2)(k)(OCH2CH2)(4)O(CH2)(12-k)H (abbreviated as CkE4C12-k) with k = 6-11 have been studied by infrared spectroscopy and differential scanning calorimetry (DSC), with focus on the effect of the position of an oligo(oxyethylene) block in the molecule. The analysis of infrared spectra has revealed that the stable molecular form changes from a fully planar structure (gamma form) to a planar/helical/planar structure (beta form) with a change of the position of the tetrakis(oxyethylene) block from the center to the end of the molecule. The DSC measurements have shown that the melting points of the gamma-form solid decrease and the melting points of the gamma-form solid increase with a shift of the tetrakis(oxyethylene) block toward the terminal of the molecule. The stabilities of the two molecular forms change over between k = 8 and 9. C8E4C4 and C9E4C3 exhibit contrasting conformational behavior with temperature; when the temperature is increased, the metastable beta form of C8E4C4 transforms into the stable gamma form, while the metastable gamma form of C9E4C3 transforms into the stable beta form. The metastable gamma form with a planar oligo(oxyethylene) block is a new finding in the present work. The experimental results of the stabilities of molecular forms are explained by the relative stabilities of partial crystal lattices formed by the alkyl and oligo(oxyethylene) blocks.