Magnetic, structural, and electric transport measurements at high temperatures were carried out on La1 -xCaxMnO3; x=0.20, 0.25, 0.30, 0.34, 0.40, and 0.45. All samples show a first-order structural phase transition from orthorhombic Pnma to rhombohedral R3̄c space group at T R-O. Magnetic susceptibility measurements show that the CurieWeiss law is strictly obeyed in the rhombohedral phase as opposed to the orthorhombic phase where the effective magnetic moment has a temperature dependence. The electrical resistivity is well described by the small polaron hopping mechanism in the samples up to x=0.34. As the charge carriers are introduced into the system (x=0.40 and 0.45), this mechanism of hopping ceases to be valid. The value of Grüneisen parameter obtained through analysis of high-resolution X-ray powder diffraction as a function of temperature increases abruptly for the sample with x=0.40. This is consistent with an increase in bending and stretchinglike frequency modes observed by Raman spectroscopy. © 2012 Elsevier B.V. All rights reserved.