Inorganic-organic hybrid semiconductors attract much more attention due to their unique characteristics of the formation of different dimensionalities of crystal structure packing and tunable optical excitonic features [1-4]. The self-assembled two-dimensional (2D) IO hybrids having general formula (R-NH₃)₂MX₄ are derived from the fundamental AMX₃ perovskite-type structure, where R is the organic moiety, M is the divalent metal (Pb²⁺, Sn²⁺, Ge²⁺, etc.), and X is the halide ion (Cl^-, Br^-, I^-) [1-5]. Weak van der Waals interaction and hydrogen bonding between organic ammonium cations (R-NH₃)⁺ and terminal halide of MX₆ part will determine the conformation and orientation of organic ammonium cation within the extended inorganic layered structure which further decides the formation of different dimensionalities (0D, 1D, 2D and 3D) of crystal structural packing [1-6]. These naturally self-assembled IO hybrid semiconductors form multiple quantum well (MQW) structure due to quantum width limit of both organic moiety (quantum barrier) and extended inorganic network structure (quantum well). The quantum confinement and dielectric screening effects are mainly responsible for the formation of stable room-temperature Mott-type excitons which enhance the exciton binding energy (200 meV~300 meV) with high oscillator strength [7, 8]. Here we present the structural dependent exciton in primary cyclic ammonium (C_nH_2n-1NH_2, n=3-8) based Inorganic-Organic hybrid semiconductors series. The linear and nonlinear optical probing of room temperature Mott-type excitons photoluminescence and absorption features demonstrate the variation from perfect 2D layered crystal packing (n=3-6) to quasi 1D structure (n=7, 8). A systematic co-existence of two kinds of excitons observable from one- and two-photon excitations are discussed and presented. One-photon induced photoluminescence (1PA-PL, ћω≥E_g) provide information about the surface excitons wherein the crystal packing of IO hybrid is perfectly aligned, however nonlinear optical pumping like two-photon excitation (2PA-PL, 2ћω≥E_g) provide comprehensive understanding of crumpled excitons present inside the interior regions of crystalline thin films and single crystal platelets due to the larger penetration depth [6, 9, 10]. The high resolution spatial and PL spectral mapping/imaging of single crystal platelets and time-resolved photoluminescence (TRPL) measurement have been performed to understand structural dependency and the existence of higher-order excitons. The transient absorption spectroscopy (TAS) measurement are also performed to understand the excited state charge carrier dynamics such as ground state bleaching (GSB), photo-induced absorption (PIA) and charge carrier recombination etc. [11-13].