The growing demand for bandwidth-hungry applications and increasing number of smart interconnected devices has increased the data traffic on radio access networks. Subsequently, the saturating spectral efficiencies in crowded radio frequency spectrum has impelled the researchers to exploit the optical spectrum for communications. In particular, many developments in the visible light communication (VLC) as a combined lighting and communications system have taken place. Despite abundant optical bandwidth, the data transmission rates and power efficiencies in VLC are partly limited by the electrical channel bandwidth and the type of signalling sets which can be used in this intensity modulated, direct detected system. In order to improve the power and spectral efficiencies, this thesis focuses on physical layer (PHY) techniques. The state-of-the-art single channel modulations (SCM) based on M-PAM, multi-channel modulations (MCM) based on OFDM, and IEEE standardised multi-colour modulations are investigated comprehensively through simulations and theoretical analysis, over representative VLC channels considering the optical properties of front-end devices. The bit error performances and spectral efficiencies of DC-biased and non DC-biased MCM systems are compared. A new vector coding based MCM is proposed to optimally utilise the channel state information at the transmitter as an alternative to optical OFDM. The throughputs, peak-to-average power ratios and DC-bias requirements of SCM and MCM systems are investigated which show that the lower DC-bias requirements reduce power consumed for the same throughput in SCM systems when compared to MCM systems. A new quad-chromatic colour shift keying (CSK) system is proposed which reduces power requirements and complexity, enhances throughput and realises a four-dimensional signalling to outperform the IEEE standardised tri-chromatic CSK system. For improved power efficiency and throughput of VLC PHY, use of rate-adaptive binary convolutional coding and Viterbi decoding is proposed along with frequency domain channel equalisation to mitigate temporal dispersion over representative VLC channels.