Along with Network Function Virtualization (NFV), Mobile Edge Computing (MEC) is becoming a new computing paradigm that enables accommodating innovative applications and services with stringent response delay and resource requirements, including autonomous vehicles and augmented reality. Provisioning reliable network services for users is the top priority of most network service providers, as unreliable services or severe service failures can result in tremendous losses of users, particularly for their mission-critical applications. In this paper, we study reliability-aware VNF instances provisioning in an MEC, where different users request different network services with different reliability requirements through paying their requested services with the aim to maximize the network throughput. To this end, we first formulate a novel reliability-aware VNF instance placement problem by provisioning primary and secondary VNF instances at different cloudlets in MEC for each user while meeting the specified reliability requirement of the user request. We then show that the problem is NP-hard and formulate an Integer Linear Programming (ILP) solution. Due to the NP-hardness of the problem, we instead devise an approximation algorithm with a logarithmic approximation ratio for the problem. Moreover, we also consider two special cases of the problem. For one special case where each request only requests one primary and one secondary VNF instances, the problem is still NP-hard, and we devise a constant approximation algorithm for it. For another special case where different VNFs have the same amounts of computing resource demands, we show that it is polynomial-time solvable by developing a dynamic programming solution for it. We finally evaluate the performance of the proposed algorithms through experimental simulations. Experimental results demonstrate that the proposed algorithms are promising, and the empirical results of the algorithms outperform their analytical counterparts as theoretical estimations usually are very conservative.