The ultrafast dynamics in vibrationally hot S1 electronic excited state in cyclopentanone molecule was discovered with time resolved spectroscopy. Investigation of the geometry change upon the S1←S0 excitation and D0←S1 ionization has shown that the dihedral angle between the C=O bond and the plane given by the carbonyl and the α-carbons is 180° either in S0 or D0 state and is reduced to 145.8° by out-out-plane deformation of the oxygen in S1 state according to the theoretical calculation. The time domain experiments with femtosecond resolution have given rich insights into the energy transfer of the cyclopentanone molecule. The molecules are excited to the vibrationally hot S1 (n, π(∗)) state following absorption of one 267-nm photon. It is found that the population of the S1 (n, π(∗)) state undergoes ultrafast internal conversion to the highly vibrationally hot S0 state within 80 fs and nonradiative deactivation by intersystem crossing to triplet T1 (n, π(*)) state occurring in 3.14 ps. Several Rydberg states have worked as stepping stones during the ionization. The available energy was distributed in the symmetric methylene group wagging and the symmetric skeletal ring breathing modes in D0 state.